We are currently sitting in the airport in Anchorage, AK awaiting our overnight flight to SC. We have had a great 2 weeks up in Alaska working with some Eskimo kids. The first week we had 28 kids (ages 8-12) come to camp. They were pretty well behaved (for the most part) and had a lot of fun. I'm not sure of the exact number of decisions that were made for Christ that week- but we heard of several stories of kids turning their lives over to Christ. The second week was a little more challenging (as was expected.) The teenagers were a little more stubborn, but not as bad as I had expected. (Praise the LORD!) We had 14 teenagers that 2nd week- so we had almost a 1:2 (camper to counselor) ratio, which was great! Andrew was a counselor both weeks for some boys, and I was the camp nurse. We had a few cuts and bruises here and there, but praise the LORD no body got really sick.
One girl in particular, Chelsea (16 years old), really tugged at some of our hearts. She (along with a lot of the other teens) is addicted to smoking and alcohol. We're not quite sure what it was, but it almost seemed like she had some sort of demonic influence in her life. Something just didn't seem right. For example, as soon as we started reading the Scriptures during our chapel time, she randomly stormed out of the room causing a big scene and threw up outside. The 2nd day into camp, several threats were made to commit suicide. So three of us counselors got to sit by her bed all night and pray and read Scripture over her. Anyways, the next day we shared some of our favorite verses with her and told her that we had been praying all night for her. She seemed to be somewhat receptive. But at the end of that day, she ended up going home because she said she couldn't stand it anymore without cigarettes and hated it here. So as the Lord brings her to mind, she could use a lot of prayer. Pray that she would continue to seek after Christ, as her only fulfillment in life. There is a missionary couple in their village- pray that they would continue to be able to reach out to Chelsea.
We are hoping to take the next several weeks to really pray about where the Lord might be calling us full time. We're hoping that by the middle of August we'll have made a decision and start the support raising process along with the preparation for the field. Thank you so much for all your prayers and support in our mission journeys!! We'll keep you updated.
praying also for wisdom for you and andrew as you wait to hear where God wants to send you!!!
I just ran across your site as I was looking up Brooks Range Bible camp and am excited to see this!! I was a counselor at Brooks Range in 2006 and now live in Alaska and am going into full time missions with Missionary Aviation Repair Center in Soldotna. I hope to make it back to Brooks Range this summer.


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Countdown to Super Bowl LI: Super Bowl XXXV
December 29th, 2016 by Bullseye Event Group
On January 28, 2001, at Raymond James Stadium in Tampa, Florida, Super Bowl XXXV was played between the Baltimore Ravens and the New York Giants.
In front of nearly 72,000 fans, the Baltimore Ravens captured their first Super Bowl trophy, defeating the Giats in dominating fashion. The Ravens showcased their stingy defense, holding the Giants to zero offensive touchdowns in the 34-7 victory.
Linebacker Ray Lewis would take home Super Bowl XXXV MVP honors, recording five total tackles and four blocked passes, the second linebacker to win Super Bowl MVP honors. The Gants would go down as history as the first team that didn't score an offensive touchdown in the Super Bowl.
The game was aired on the CBS network and brought in a total 84.3 million views. The National Anthem was sung by the Backstreet Boys and halftime was brought to the crowd by Aerosmith. There were a ton of announcers for this game, Phil Simms and Greg Gumbel to name a few. The cost of a 30 second commercial for Super Bowl XXXV was $2.1 million, which is way more than any of the early Super Bowls ever cost.
Want to check the Super Bowl off your bucket list? Travel packages to Super Bowl LI in Houston are available now! Including some of the most luxurious hotels in Houston, a ticket to the 2017 Players Tailgate featuring America's favorite chef, Guy Fieri, and a ticket to the big game!
Indianapolis Colts Week 16: Eliminated »
« Countdown to Super Bowl LI: Super Bowl XXXVI

redpajama_set_name: RedPajamaCommonCrawl


Shimla is one of the most beautiful tourist spots blessed with blissful Shimla capital city of Himachal Pradesh State is an all time favorite of tourists from all over the country. Millions of travelers rush to this majestic hill station during snow season to experience the thrill of snow fall in Shimla. December January months are the best season to enjoy the snow fall in Shimla. The hill station of Shimla has a cool climate with cold waves are rare. Snowfall is quite often and on average it falls for every week during December and Januarys. Night temperature drop below freezing December and may drop to about -2 °C. Snow fall doesn't need snow to settle on the plain areas as there is a blanket of white powder on the streets of Shimla. As Shimla is a popular snow destination travelers want to know when and where will snow hit Shimla ? People often enquire will snow fall in Shimla ? Snowfall covers most parts of the Shimla including the popular Mall Road and Lakkad Bazar areas. December last week Shimla witnesses endless deep snow everywhere all within quick and easy reach. Shimla looks extremely beautiful during winter seasons. So treat yourself to this snow experience with your family and dear ones.
Skiing, Snowboarding on the slopes, walking along the frozen lakes and enjoying fresh snow fall are the popular snow activities in Shmila. Shimla is known for its cool climate and cool climate. Visiting Shimla during snow fall season is truly a unique experience. The snow is deep and slushy and need to be careful while indulging in adventure activities. Whether you want to indulge in snow games, snow man and other games for children or just enjoy fresh snow fall, we have the ideal holiday arrangements for you. If you are searching for a change from the snow activities, we can provide you wide range activities away from the slopes.
If you are keen to experience snow in Shimla and spend some time amid the valleys draped with snow, then you should plan your trip between December to February. These are the three most likely months to experience snow in Shimla. Although March and April are not big snow months and snowfall is extremely rare, it is better to be prepared to deal with snow during these months as well.
The best season to enjoy snow fall would be during the extreme winter season- from December last week to January 2nd week. Normally tourists from neighboring states rush to this hill station during Christmas and New Year eve to play with snowflakes by throwing snow balls.
A lot of gear involved when it comes snow games. Weather in mountain can change very fast which can make dressing appropriately difficult. If you want to play in the snow for a long time you need to wear the right kind of snow boots. Always dress with good quality thermal layers inside and pants and water proof jackets to keep you dry. Always wear muffler, caps and neck warmer to cover your nose and mouth for protection from cold waves.


Though I have known her since childhood, this post was completely unsolicited. The end. ENJOY.
Here are some of her awesome images. They are a heavy dose of inspiration.
She is fine art meets jedi master. Yes. Oh yes. See more here.
and sneaking out of our houses to go to Denny's in P-Town.
Where did those days go?


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Sprout Blog / Case Studies
How the Urban Institute Boosts Messaging Reach Through Sprout Social and Bambu
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YoY increase in organic Twitter impressions
YoY increase in total Twitter followers
YoY increase in Twitter messages received
The Urban Institute believes facts matter and evidence has the power to strengthen communities and improve lives.
The Washington, D.C.-based nonprofit produces original research—crunching numbers, sharing data with the public and providing recommendations to decision makers and influencers.
And it turns to social media to help spread the word.
Since signing on with Sprout Social and Bambu, the Urban Institute has experienced consistent boosts in messaging reach. Over the past year alone, the organization achieved a 12% increase in total social followers, resulting in more than:
13 million impressions
160,000 engagements
62,000 link clicks
Additionally, the Urban Institute captured a total potential reach of over a million social users thanks to employee advocates.
Capturing Attention
According to Nicole Levins, Senior Digital Communications Manager at the Urban Institute, the organization works with hundreds of researchers covering a wide range of issues, from health care to taxes to housing finance.
The information it uncovers and shares is of great interest to lawmakers and other individuals shaping policy, and is delivered in a nonpartisan fashion.
"For example, if a new law is proposed at the federal level, we wouldn't say this is bad or don't vote for this," Levins said. "But we might say, 'Here's what could happen if you enact this. We have research on this, and this is what the research says.' We're just trying to bring evidence to bear on policy conversations that are happening."
For the Urban Institute, online fundraising is a secondary goal. The organization operates more as a publisher than fundraiser, and its audience is policymakers, major media outlets and the people who work in the spaces it researches.
However, staying above the political fray comes with drawbacks.
"We don't do any advocating ourselves, which can actually make our social media work more challenging," Levins said. "In essence, we're saying, 'Here are some interesting facts, do with them what you will.' It can be harder for social, because you're not making really strong statements, and you're not telling people to do something, or to get angry, or explicitly telling them something is bad. And people tend to get more excited about that."
Fortunately, through a combination of smart social strategy and employee advocacy supported by Sprout Social and Bambu, the Urban Institute is able to amplify its message and reach its target audiences.
Expanding Reach
Levins knew the Urban Institute needed social media management tools to succeed, but was less than impressed with what the organization was using.
"We were already using a tool when I started in 2013, and I hated it," Levins said. "I did a month-long trial of Sprout and loved it. I was afraid the transition from an old platform to a new one would be really hard, but it was so easy. And once we learned about Bambu, it seemed like an easy way to support our social efforts even more. It was easy to integrate it with our current strategies and better engage our staff."
Publishing and social media monitoring are primary concerns for the Urban Institute. With Sprout's publishing features, the organization is able to automatically post content across all connected social profiles at optimal times to maximize reach, and can then monitor who is sharing and commenting on its content. Beyond generating awareness, the organization wants to be able to identify online influencers and key stakeholders.
"I couldn't do my job without Sprout," Levins said. "When I get in in the morning, I can schedule a handful of posts, set it and forget it. And throughout the day, I check back in and update and respond as necessary."
While it's active on Facebook, LinkedIn and Instagram, Twitter is the organization's social channel of choice. Year over year on Twitter, as of April 16, 2018, the Urban Institute saw a:
6.8% increase in organic impressions.
10.3% increase in total followers.
15.1% increase in messages received.
Meanwhile, Bambu has helped the Urban Institute organize its employee advocacy efforts, opening the door to further increases in online reach. Levins is able to curate content employees can quickly and easily share on their personal social profiles.
Year over year, thanks to employee advocacy on Bambu, the Urban Institute achieved a total potential reach of 1,034,903 across Facebook, Twitter and LinkedIn. This growth has continued month over month as well, with total employee story shares increasing 200% between March and April 2018.
Employee shares are especially effective at maximizing messaging reach, as data shows brand messages shared by employees reach 561% further than those shared by brand social channels, and are also re-shared 24 times more frequently.
The Urban Institute's tagline is "Elevate the debate." With Sprout Social and Bambu, it can do just that by ensuring its work is shared far and wide.
Social Media Publishing
Social Media Scheduling
View All More resources for youMore resources for you
Sprout Social is a breath of fresh air for Inspire Medical Systems
Sprout Social outfits River Island for success on social media


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Q: How to resolve "Error: Cannot find module 'gulp-browserify'" I tried to run my files with gulp, and it showed:
Last login: Fri Dec  5 11:09:12 on ttys001
Macs-MacBook-Pro:responsive mac$ gulp
Error: Cannot find module 'gulp-browserify'
    at Function.Module._resolveFilename (module.js:338:15)
    at Function.Module._load (module.js:280:25)
    at Module.require (module.js:364:17)
    at require (module.js:380:17)
    at Object.<anonymous> (/Users/mac/Desktop/responsive/gulpfile.js:3:18)
    at Module._compile (module.js:456:26)
    at Object.Module._extensions..js (module.js:474:10)
    at Module.load (module.js:356:32)
    at Function.Module._load (module.js:312:12)
    at Module.require (module.js:364:17)

What should I do?
Thanks.

A: I've just reinstalled gulp (and all required modules) globally and locally; like:
sudo npm install -g gulp gulp-watch gulp-stylus gulp-file-include browser-sync kouto-swiss gulp-browserify browserify

and then in project folder:
npm install gulp gulp-watch gulp-stylus gulp-file-include browser-sync kouto-swiss gulp-browserify browserify

and that helped for me

redpajama_set_name: RedPajamaStackExchange


03/103/13 I was also told by the guys at Best Buy that Metranow has a dash kit that allows new stereos to be installed higher in the dash,where the factory stereo was mounted, which improves the line of site to thenew stereo. Metra still makes the olderdash kit that mounts the stereo unit closer to console for the shifter **** of thevehicle. The only downside is that itcosts approx. $300. I had alreadypurchased and installed the older kit from Metra, so my new stereo is mountedlow and closer to the shifter console. Ithink it is just fine mounted at the lower location, especially since the clockin my factory stereo now serves as my clock, and I use the display of my newstereo exclusively to display the radio station/CD track information. Hope this is helpful to fellowdo-it-your-selfers!
03/03/12 On a similarnote, to get the lights for existing heating, A/C and stereo/clock toilluminate, purchase a reverse (male) harness (Metra 71-1721) throughsonicelectronix.com for $12, and plug it into the back of the factory stereoand wire to correct illumination wires for the climate control buttons on thedash. Rather than dismantling thedashboard again after I installed my new car stereo myself, I took my car to toBest Buy, where they wired it for $21 including tax. Works great. It was not real safe to operate the vehicle at night, while trying toadjust heating and A/C until I did this.
Hi All...New member in need of suggestions.
Quick Reply: New Stereo Suggestions?


Canada. Royal Canadian Navy -- Registers.
Canada. Marine royale -- Registres.
Issues reproduced: Feb., Dec. 1926; June 1927; Feb., Nov. 1929; July 1930; Jan., July 1931; Jan. 1932; Jan., Sept. 1933; Sept. 1934; Jan., Aug. 1936; Feb., Sept. 1937; Apr., Oct. 1938; Oct., Nov. 1939; Apr., Aug. 1940; June 1946; June, Dec. 1947; July 1948; July 1949.


Should the U.S. Adopt the "Right to be Forgotten" Online?
I took part in a really fun Intelligence Squared debate for public radio last night. The resolution was "The U.S. Should Adopt The 'Right To Be Forgotten' Online." My partner was Harvard Law professor Jonathan Zittrain. We opposed the resolution, arguing that the EU's newly-minted "right to be forgotten" is a pernicious form of censorship that buries truth, is prone to abuse, and cannot justly be administered. On the other side were Eric Posner, professor of law at the University of Chicago, and Paul Nemitz, director of fundamental rights and citizenship at the European Commission's Directorate General for Justice & Consumers.
Who won? I'm not too classy to report that Jonathan and I (or, more accurately, the arguments we advanced) won the debate overwhelmingly, as judged by the audience. Go free speech!
Video of the debate is here. Audio is here.


Keep dry and protected even in a downpour with the Ultimate Terrain Unisex Pack-In Rain Suit. Both the jacket and the pant are constructed of rugged, flexible 100% EVA material with fully welded seams for reliable waterproof performance. The jacket features an attached hood with drawstring adjustment; full-zip closure, front placket; elastic-bound cuffs; and lower-front pockets with snap-closed flaps. The rain pant features a full elastic waistband. Unisex design. Imported.


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Rosh Hashanah Greetings and Answers From Cute Kids in Delaware JCC
We're being indundated with new Internet videos relating to Rosh Hashanah, which arrives next Wednesday evening. They come in many forms -- original music videos, parodies of pop songs, and calls for reflection and self-improvement by rabbis and other serious Jews.
We've shared a few that we think are the most entertaining and still have a few more to go. But today we're sharing a video from another source that should be heard from -- preschool children. There's nothing like the answers these kids give to the basic questions you'd ask about the holiday.
Here are the questions posed to the kids of the Early Childhood Center of the Delaware JCC and their cute and funny answers:
What is Rosh Hashanah?
What do you like to eat on Rosh Hashanah?
Why do we eat apples and honey?
What do you do on Rosh Hashanah?
Where is Israel?
What do you want to wish Israel for Rosh Hashanah?
What are your wishes for the New Year?
Can you sing us a song for Rosh Hashanah?
Labels: Jewish Life, Kids, Rosh Hashanah, Videos
Aviva W Friday, September 19, 2014 at 1:16:00 PM EDT
How lovely. Children are beautiful.


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6ix9ine Won't Troll Now That He's Back on Social Media, Says Lawyer
Pietro D'aprano, Getty Images
6ix9ine made an appearance on social media over the weekend, but won't be returning to his old trolling ways.
Tekashi, who was officially released from prison on Thursday (April 2) due to the coronavirus pandemic, will be allowed to use social media while finishing out his prison sentence on home confinement. However, TMZ reports that although 6ix9ine has been permitted internet access, the rapper will have to be mindful of what he posts because his probation officer will be surveilling his accounts.
On Monday morning (April 6), Lance Lazarro, an attorney for 6ix9ine, confirmed to XXL that the rapper will not be trolling or starting feuds with other rappers on social media because his accounts are being monitored.
Ironically, 6ix9ine appeared in The Shade Room's Instagram comments on Sunday (April 5) under a post revealing that Los Angeles' mayor was offering rewards to people who were willing to tell on their neighbors for disobeying the city's stay-at-home order.
TheShadeRoom via Instagram
"Coming to the rescue," Tekashi wrote in his first social media comment since being released from prison.
6ix9ine received approval to serve the remainder of his sentence at home last Thursday due to his asthma condition, which would have made his battle against the coronavirus difficult if he was to contract the illness while in prison.
Hours after it was revealed that Tekashi was going to be released early, the rapper's other attorney, Dawn Florio, confirmed to XXL that not only will he be allowed back on social media, but 6ix9ine will also be working on new music. This new music includes both a Spanish and an English album.
See 22 Hip-Hop-Related Police Raids
Source: 6ix9ine Won't Troll Now That He's Back on Social Media, Says Lawyer
Filed Under: 6ix9ine


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Don't Be The Best (Be Good Enough Instead)
A while back a buddy of mine sent me this text...
You see everybody wants to be "the best" at what they do in career and business.
When you focus on trying to be the best there are 4 key consequences that people fail to realize.
But when you...
3 Tips To Start A Business In A Saturated Market
Are you afraid to start a business because you feel that the topic or niche you're serving is an oversaturated market?
Are you stuck in a business that you've already started and think it's because of market saturation?
What if I told you that...
Elon Musk Says Work Every Waking Hour
There's this "motivational" video on YouTube that's a compilation of Elon Musk interviews (billionaire founder of Tesla and Space X) called WORK EVERY WAKING HOUR.
In it Musk actually shares some fascinating thoughts that...
Stop Looking At The Numbers
In a world of powerful data and analytics tools at our fingertips, could looking at the numbers actually be hurting our business and growth potential?
I mean, the quote goes: "What gets measured, gets managed" right?! Maybe.
Today, I want to...
Multiple Streams Of Income: How I Earn Money 10 Different Ways
I've always heard the average millionaire has 7 or more streams of income. Meaning they earn income from 7 different sources.
As compared to say the average worker in America which has exactly one stream of income - their job.
Over the...
Online Business In 2020: Don't Make These 3 Mistakes
Things ain't what they used to be when it comes to online business.
If you are running or building your business and presence online in 2020 like many of us did in the past 5 years you probably won't hit your income goals this year.
Ask This Question Every New Year
Can I share something super helpful with you today?
As the New Year rolls in and everyone is excited about making resolutions and becoming a better person, I feel like there is a huge missed opportunity.
Instead of announcing bold new goals to...
Give Before You Sell
So it's Christmas Eve today and hopefully you're spending time with family and friends. But that doesn't mean I can't hook you up with a new video!
In fact - in the spirit of Christmas and the focus on giving I think today is a great opportunity...
Why Slow And Reliable Growth Wins
Which would you rather have: a $1 Million product or a $1 Million launch?
It's kind of a trick question as million-dollar launches are virtually impossible for most people to pull off and can create a TON of stress and pressure if the revenue is...
Run Your Own Race In Business
How often do we get tripped up in business (and life) because we are trying to run someone else's race and not our own?
How often does comparison and jealousy lead down the path of wasted time and discontentment?
What would it look like in 2020...


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Acid-modified clinoptilolite as a support for palladium–copper complexes catalyzing carbon monoxide oxidation with air oxygen
Tatyana L. Rakitskaya1,
Tatyana A. Kiose1,
Kristina O. Golubchik1,2,
Alim A. Ennan2 &
Vitalia Y. Volkova1
Chemistry Central Journal volume 11, Article number: 28 (2017) Cite this article
Samples of natural clinoptilolite were modified by an acid–thermal method at nitric acid concentrations of 0.25, 0.5, 1.0, and 3.0 M and a contact time of 30 min. A series of catalysts, K2PdCl4–Cu(NO3)2–KBr/S (S = 0.25H-CLI, 0.5H-CLI, 1H-CLI, and 3H-CLI) was obtained. All samples were investigated by X-ray phase and thermogravimetric analysis, FT-IR spectroscopy, water vapor ad/desorption and pH metric method. Besides, K2PdCl4–Cu(NO3)2–KBr/S samples were tested in the reaction of low-temperature carbon monoxide oxidation. It have been found that, owing to special physicochemical and structural-adsorption properties of 3H-CLI, it promotes formation of the palladium–copper catalyst providing carbon monoxide oxidation at the steady-state mode down to CO concentrations lower than its maximum permissible concentration at air relative humidity varied within a wide range.
Natural clinoptilolite is a material most commonly used for both water vapor and gaseous toxicant adsorption, gas separation, wastewater treatment. It is also used as an acid catalyst in oil processing and a support for catalytically active phase in the case of catalysts for redox reactions of CO, SO2, and O3 [1,2,3,4,5,6]. Catalytic activity of clinoptilolite supported palladium–copper complexes has been found to depend considerably on physicochemical properties and structural parameters of a support affecting a composition of these surface complexes [4, 5]. For optimizing clinoptilolite behavior, one can modify it thermally as well as by treatment with water, acid or alkali at both room and higher temperatures. An effectiveness of the mostly used acid–thermal treatment depends on the nature and concentration of acid applied, a period of interaction between the acid and clinoptilolite (a contact time), and a solid:liquid ratio [7,8,9,10,11,12,13,14,15,16]. The acid–thermal modification of clinoptilolite results in a substantial increase in both a Si:Al ratios and its surface acidity [1]. There are also changes in adsorption capacity towards metal ions [17, 18] and water vapor [12, 19], in thermochemical properties [10], in relative crystallinity [13], and in sizes of crystallites [8, 12], and also in structural-adsorption parameters such as a specific surface area (Ssp), sizes and volumes of pores [7,8,9,10,11,12,13,14,15].
Properties of acid-modified clinoptilolites of different origin were investigated in many works whereas catalysts composed of clinoptilolite and anchored d metal ions or salts and used for catalyzing redox processes are objects of only few studies. For instance, Ni2+/CLI is applied for sulphur removal from fuel oil [18], Ag+/CLI [20], Cu2+(Zn2+, Mn2+)/CLI [21], Mn2+(Co2+, Cu2+)/CLI [22, 23] are used for ozone decomposition, K2PdCl4–Cu(NO3)2–KBr/H-CLI and CuCl2/CLI are proposed by us for the oxidation of carbon monoxide [4,5,6, 24] and sulfur dioxide [25], respectively.
Although natural zeolites, including clinoptilolite, are commonly used for water vapor adsorption [26,27,28], adsorption of water vapor by clinoptilolite modified with acid [1, 12, 26] or transition metal ions (complexes) [6, 29, 30] is little-studied. However, it has been found by us [31, 32] that a composition and catalytic performance of surface palladium–copper complexes in some redox processes, namely, carbon monoxide and phosphine oxidation, significantly depend on a thermodynamic activity of water adsorbed on them (\( a_{{{\text{H}}_{2} {\text{O}}}} \) = P/PS). This parameter was determined from isotherms of water vapor adsorption and proved to be necessary for both obtaining catalysts of optimal composition and their applying in respiratory and environment protection.
Mostly, for clinoptilolite modification, hydrochloric or sulfuric acid [7,8,9,10,11,12,13,14] and, more rarely, phosphoric [33] or nitric [3, 4, 15] acid are used. Our choice of nitric acid as a modifying agent is caused by the following circumstance. Adsorbability of ions in the case of clinoptilolite decreases in the order Cl−≫SO4 2−>NO3 − [34], so, some amounts of chloride and sulfate ions can remain after their desorption by water and, consequently, these residual chloride and sulfate ions, becoming ligands, can decrease the activity of supported palladium–copper complexes [31, 32].
As a rule, acid treatment is used for changing physicochemical and structural-adsorption properties of clinoptilolite. Depending on the aim of a research, acid concentrations may be varied in a wide range [7, 12, 16]. To prepare anchored palladium–copper complexes characterizing by the maximum catalytic activity towards carbon monoxide oxidation, it is necessary to choose an acid concentration optimal for each specific support [35, 36].
The aim of the work is to ascertain how nitric acid concentrations used for clinoptilolite modification affect its physicochemical and structural parameters as well as the catalytic activity of modified clinoptilolite anchored palladium–copper complexes in the reaction of low-temperature carbon monoxide oxidation with air oxygen.
In the work, as in our earlier studies [4, 24], natural clinoptilolite, N-CLI, from Sokirnytsia deposit (Trans-Carpathian region, Ukraine) was used. Acid-modified samples were prepared as follows: 50 g of N-CLI with a grain size of 0.5–1.0 mm were boiled in 100 mL of nitric acid solution with concentrations of 0.25, 0.5, 1.0 or 3.0 mol L−1 for 30 min. Then, the samples were washed with bidistilled water till a negative reaction for NO3 − ions. The obtained samples denoted as 0.25H-CLI, 0.5H-CLI, 1H-CLI and 3H-CLI, respectively, after their air-drying at 110 °C till constant weight, were used for preparation of catalysts by the following procedure: 10 g of each support were subject to incipient wetness impregnation with aqueous solution containing certain amounts of K2PdCl4 Cu(NO3)2, and KBr. Loose wet samples obtained were aged in Petri dishes at room temperature for 20–24 h, air-dried in an oven at 110 °C till constant weight, and, finally, cooled in a desiccator over concentrated H2SO4. As a result, the contents of K2PdCl4, Cu(NO3)2, and KBr in all catalyst samples were 2.72 × 10−5, 5.9 × 10−5, and 1.02 × 10−4 mol g−1, respectively.
X-ray phase analysis of the samples was carried out with the help of a Siemens D500 diffractometer in CuK α radiation (λ = 1.54178 Å) with a secondary beam graphite monochromator. After thorough grinding, the samples were placed into a glass cell (2 × 1 × 0.1 cm3). XRD patterns were collected in 2θ region from 3° to 70° with a step size of 0.03° and an accumulation time of 60 s at every point.
FT-IR spectra were recorded by a Perkin Elmer FT-IR spectrometer (the detection region of 400–4000 cm−1 and resolution of 4 cm−1). A mixture consisting of a material under study (1 mg) and KBr (200 mg) was compressed under pressure of 7 tons cm−2 for 30 s.
A thermogravimetric (DTG–DTA) investigation of the samples (0.25 g) was carried out by a Paulik, Paulik and Erdey derivatograph at a heating rate of 10 °C/min in the temperature range from 20 to 1000 °C with an accuracy of ±5%.
Water vapor ad/desorption by samples of natural and modified clinoptilolite was studied in a vacuum setup with a McBain silica-spring balance thermostated at 21 °C. As a preliminary, the samples (1.0–2.0) × 10−4 kg were air-dried at 110 °C till constant weight. Their evacuation was carried out by a fore pump and an oil-vapour diffusion pump for several hours. Residual pressure was monitored by a VIT-2M ionization-thermocouple vacuum meter. A first and following water vapour pumpings were realized till a constant weight attainment. A period of equilibrium achievement for these samples was ca. 24 h. The partial pressure of air was measured with an accuracy of ±2.6 Pa by a U-tube mercury manometer. Both a change in the sample weight caused by adsorption and differences in a U-tube mercury manometer level were measured by a KM-6 cathetometer. Its accuracy was ±2%.
To characterize protolytic properties of surface functional groups, 0.2 g of natural clinoptilolite or its acid-modified samples were suspended in 20 mL of bidistilled water and an equilibrium pH value was measured by a pH-340 instrument equipped with an ESL 43–07 glass electrode and an EVL 1M3 chlorsilver electrode at continuous stirring of the suspension at 20 °C. A suspension effect, ∆pHs, was estimated using the following equation
$$ \Delta {\text{pH}}_{\text{s}} = {\text{ pH}}_{\text{st}} {-}{\text{ pH}}_{0} $$
where pH0 and pHst are pH values of a suspension measured in 15 s and after the equilibrium attainment.
A catalytic activity of the samples in the reaction of CO oxidation was tested in a gas flow setup with a fixed-bed glass reactor at 20 °C. A size of the reactor, an approximate size of catalyst grains, dg, equal to 0.75 mm and a linear velocity of gas–air mixture (GAM), U, equal to 4.2 cm s−1 fit with the requirements to a kinetically controlled reaction.
A GAM with the initial carbon monoxide concentration, \( {\text{C}}_{\text{CO}}^{\text{in}} \), of 300 mg m−3 was prepared by attenuation of the concentrated (98–99%) CO with air pre-purified by a tandem filter containing active carbon of SKN-K rank and fibrous filtering material of FP type. \( {\text{C}}_{\text{CO}}^{\text{in}} \) and a final carbon monoxide concentration, \( {\text{C}}_{\text{CO}}^{\text{f}} \), were measured by a 621EKh04 gas analyzer (Ukraine) with a minimum detectable CO concentration of 2 mg m−3.
The reaction rate, W, is evaluated by the equation:
$$ {\text{W}} = \frac{{{\text{w}}\left( {{\text{C}}_{\text{CO}}^{\text{in}} - {\text{C}}_{\text{CO}}^{\text{f}} } \right)}}{{{\text{m}}_{\text{c}} }},\;{{\text{mol}} \mathord{\left/ {\vphantom {{\text{mol}} {\left( {{\text{g}}\times{\text{s}}} \right)}}} \right.} {\left( {{\text{g}}{ \times }{\text{s}}} \right)}} $$
where w = 1.67 × 10−2 is a volume flow rate of the GAM (L/s), \( {\text{C}}_{\text{CO}}^{\text{in}} \) and \( {\text{C}}_{\text{CO}}^{\text{f}} \) are initial and final CO concentrations (mol/L), respectively, and mc is a weight of the catalyst sample (g).
A reaction rate constant for steady-state portions of kinetic curves is determined by the equation
$$ {\text{k}}_{\text{I}} = \frac{1}{{{\tau^{\prime}}}}\ln \frac{{{\text{C}}_{\text{CO}}^{\text{in}} }}{{{\text{C}}_{\text{CO}}^{\text{f}} }} , {\text{s}}^{ - 1}$$
where τ′ is an effective residence time, calculated as a ratio of a catalyst layer height to a linear velocity of the GAM.
An experimental amount of oxidized CO, Qexp, is determined based on experimental \( \Delta {\text{C}}_{\text{CO}}^{\text{f}} \)vs. τ plots. A percentage of CO conversion at the steady-state mode, ηst, and a stoichiometric coefficient, n, per 1 mol of Pd(II) (a number of full catalytic cycles) are calculated by the equations
$$ \eta_{st} = \frac{{\left( {{\text{C}}_{\text{CO}}^{\text{in}} \text{ - }{\text{C}}_{\text{CO}}^{\text{f}} } \right)}}{{{\text{C}}_{\text{CO}}^{\text{in}} }}{ \times }100,{\% }, $$
$$ n = {{{\text{Q}}_{ \exp } } \mathord{\left/ {\vphantom {{{\text{Q}}_{ \exp } } {{\text{Q}}_{\text{Pd(II)}} }}} \right.} {{\text{Q}}_{\text{Pd(II)}} }}, $$
where QPd(II) is an amount of palladium(II) contained in the sample.
X-ray characterization
Figure 1 shows X-ray diffraction patterns of the samples under study recorded in the 2θ region from 0° to 40° because the most intense reference reflections (2θ (d, Ǻ)) for clinoptilolite phase: 9.865° (8.959), 22.416° (3.963), 30.057° (2.970) and α-SiO2 phase: 20.848° (4.257), 26.613° (3.346) are located in this region. The XRD patterns of N-CLI, H-CLI, and Pd(II)–Cu(II)/H-CLI samples were analyzed based on the three reference reflections of the clinoptilolite phase.
XRD patterns for natural (1) and acid-modified 0.25H-CLI (2), 0.5H-CLI (3), 1H-CLI (4), and 3H-CLI (5) clinoptilolite samples as well as: Pd(II)–Cu(II)/0.25H-CLI (6), Pd(II)–Cu(II)/0.5 H-CLI (7), Pd(II)–Cu(II)/1H-CLI (8), and Pd(II)–Cu(II)/3H-CLI (9) catalysts
X-ray spectral parameters, i.e. an interplanar spacing d (Ǻ), a normalized relative intensity, IN, and a relative crystallinity, IR (%) of the samples are summarized in Table 1. IR values were calculated using the procedure described elsewhere [9] as a ratio of the sum of IN values for the three reference reflections taken from XRD patterns of the acid-modified clinoptilolite samples to the sum of those values for N-CLI.
Table 1 X-ray spectral parameters for N-CLI, H-CLIs, and Pd(II)–Cu(II)/H-CLIs
In the case of Pd(II)–Cu(II)/H-CLI samples, IR was determined as a ratio of the sum of IN values for them to the sum of IN values for the corresponding acid-modified clinoptilolite samples. The data presented in Table 1 show that the most significant effect of a nitric acid concentration on IR takes place for \( {\text{C}}_{{{\text{HNO}}_{ 3} }} \) = 3.0 mol L−1 when the relative crystallinity value goes down to 84% in the case of the 3H-CLI sample and to 56% for the Pd(II)–Cu(II)/3H-CLI one. Deviations observed for the first reference reflection that is usually most sensitive to any structural changes are very slight (0.004–0.017 Ǻ).
Thus, one can deduce that the acid–thermal modification of natural clinoptilolite with nitric acid at its concentration within the range of 0.25 to 3.0 mol/L and the following Pd(II) and Cu(II) anchoring result in some changes in the clinoptilolite structure with no collapse in its framework Moreover, the absence of new X-ray diffraction peaks indicate that no new crystalline phase formed by Pd(II) and Cu(II), i.e. their salts or oxides (PdO, Cu2O, CuO) or reduced forms (Pd0 or Cu0), appears.
FT-IR characterezation
Figure 2 shows portions of FT-IR spectra recorded for N-CLI, H-CLIs, and Pd(II)–Cu(II)/H-CLIs in two regions i.e. 4000–3000 and 1900–400 cm−1 because these regions contain the bands characteristic of natural clinoptilolite belonging to the seventh structural group [38]. Results of the FT-IR spectra interpretation are summarized in Table 2.
IR spectra for natural (1) and acid-modified 0.25H-CLI (2), 0.5H-CLI (3), 1H-CLI (4), and 3H-CLI (5) clinoptilolite samples as well as: Pd(II)–Cu(II)/0.25H-CLI (6), Pd(II)–Cu(II)/0.5H-CLI (7), Pd(II)–Cu(II)/1H-CLI (8), and Pd(II)–Cu(II)/3H-CLI (9) catalysts
Table 2 Wave numbers (cm−1) of absorption band maximums in FT-IR spectra of N-CLI, H-CLIs, and Pd(II)–Cu(II)/H-CLIs
All FT-IR spectra demonstrate a wide complex-shaped band at νOH 3440–3484 cm−1 which center for 3H-CLI shifts by 24 cm−1 in comparison with N-CLI. This band characteristic of stretching vibrations of OH groups in associated water molecules is asymmetrical and its high-frequency component has a clearly detectable shoulder at 3628 cm−1 (N-CLI) remainder after the acid treatment and caused by a bridge SiO(H)Al group. Pd(II) and Cu(II) anchoring is accompanied by a low-frequency shift of νOH indicating a perturbation in hydrogen bonds and a change in their energy induced by metal ions. A band at 1633 cm−1 characterizing deformation vibrations of water molecules for N-CLI demonstrates a slight high-frequency shift with the increase in acid concentration, however, it remains unchanged for the samples containing anchored palladium and copper ions (Table 2). A very intense and wide complex-shaped band in the region of 1250–980 cm−1 is a superposition of several bands attributed to vibrations of Si–O–Si and Si–O–Al fragments [39].
In the FT-IR spectrum of N-CLI, it is situated at 1064 cm−1 and has a shoulder at 1205 cm−1. In the FT-IR spectra of the acid-modified samples, the shoulder is in the same position but a center of the band shifts to a high-frequency region and the maximum shift of 17 cm−1 is found for 3H-CLI. Pd(II) and Cu(II) anchoring doesn't change a position of this band in comparison with the corresponding support. For all samples under study, there is no change in positions of the other bands.
The data obtained indicate that, judging from the high-frequency shift of the Si–O–Al band, significant changes in the Si–O–Al structural fragment due to the clinoptilolite dealumination take place after its half-hour acid treatment already at \( {\text{C}}_{{{\text{HNO}}_{ 3} }} \) > 0.5 mol L−1. Pd(II) and Cu(II) anchoring doesn't lead to any changes in the frequencies of stretching vibrations of structural groups in the aluminosilicate framework because of low concentrations of these metal ions.
Thermogravimetric characterization
Figure 3 shows differential TGA curves for N-CLI, H-CLI and Pd(II)–Cu(II)/H-CLI samples. Dehydration of the samples is characterized by only one endothermic effect and the temperature corresponding to its maximum coincides with the maximum of its DTG curve. The results of the thermogravimetric analysis are presented in Table 3.
TGA curves for natural (1) and acid-modified 0.25H-CLI (2), 0.5H-CLI (3), 1H-CLI (4), and 3H-CLI (5) clinoptilolite samples as well as: Pd(II)–Cu(II)/0.25H-CLI (6), Pd(II)–Cu(II)/0.5H-CLI (7), Pd(II)–Cu(II)/1H-CLI (8), and Pd(II)–Cu(II)/3H-CLI (9) catalysts
Table 3 Results of the thermogravimetric analysis of natural and modified clinoptilolite samples
One can see that the modification of natural clinoptilolite under above mentioned conditions has no substantial influence on TM values. Besides a total weight loss equal to 10–13% for all samples. Weight loss values were estimated for temperature ranges of 25–110 and 25–300 °C in order to quantify specific amounts of water (m \( _{{{\text{H}}_{2} {\text{O}}}} \)) remained in the samples after their air-drying at 110 °C which are ranged from 2.7 to 3.3 mmol g−1.
Water vapor ad/desorption
Isotherms of water vapor ad/desorption shown in Fig. 4, are S-shaped and have a clearly defined loops of the capillary condensation hysteresis closed at P/Ps < 0.25. Forms of adsorption and desorption branches are similar indicating that the porous structures of the samples don't change after their exposure to water vapor.
Water vapor adsorption (○) and desorption (●) isotherms for natural (1) and acid-modified 0.25H-CLI (2), 0.5H-CLI (3), 1H-CLI (4), and 3H-CLI (5) clinoptilolite samples as well as: Pd(II)–Cu(II)/0.25H-CLI (6), Pd(II)–Cu(II)/0.5H-CLI (7), Pd(II)–Cu(II)/1H-CLI (8), and Pd(II)–Cu(II)/3H-CLI (9) catalysts at t = 21 °C. Curves 2–5 and 7–9 are shifted one from another by 0.5 P/Ps
All isotherms obtained by us were analyzed using a linear form of BET equation realized up to P/Ps ≤ 0.3 with correlation coefficient R2 of 0.98–0.99. A monolayer capacity, a m, a constant characterizing an affinity between given adsorbate and adsorbent, C, and a specific surface area of the samples, Ssp, estimated according the procedure described elsewhere [19], are presented in Table 4. Values of a thermodynamic activity of adsorbed water, \( a_{{{\text{H}}_{2} {\text{O}}}} \), were determined from the adsorption isotherms shown in Fig. 4 at adsorption values, a, equal to the monolayer capacities.
Table 4 Structural-adsorption parameters of natural and modified clinoptilolite samples
The data presented in Table 4 show that, in comparison with the parameters obtained for N-CLI, values of a m and Ssp increase and C values diminish with \( {\text{C}}_{{{\text{HNO}}_{ 3} }} \) increasing from 0.25 to 3.0 mol L−1 in the case of the acid-modified samples. From literature [6,7,8,9,10,11,12,13,14,15,16], it can be seen that a specific surface for acid-modified clinoptilolite significantly depends on an acid concentration, time and multiplicity of treatments, and a solid:liquid ratio. As a rule, Ssp increased or attained its maximum value with an acid concentration and only once (Ssp determination based on water vapor adsorption) [12], it decreased from 383 to 273 m2 g−1 when CHCl was heightened from 0.16 to 5.0 mol L−1 at the temperature of 100 °C.
In comparison with N-CLI, the \( a_{{{\text{H}}_{2} {\text{O}}}} \) value markedly diminishes only for 3H–CLI. The anchored palladium–copper complexes don't affect the structural-adsorption parameters of the corresponding acid-modified clinoptilolite samples and their water activity values owing to low concentrations of these metal ions.
pHs characterization
Acid modification of clinoptilolite leads to a drastic change in its protolytic properties that can be quantified by measuring pH of its aqueous suspension. Table 5 summarizes these pH values for N-CLI and H-CLI samples.
Table 5 PH values for suspensions of natural and acid-modified clinoptilolite samples
A directional change in pH values indicates a type of aprotonic sites. For natural clinoptilolite, ΔpHs > 0 showing a prevalence of Lewis basic sites, whereas for acid-modified clinoptilolite forms, ΔpHs < 0, being evidence of a prevalence of Lewis acid sites. Already in the case of 0.25 HNO3, pHst lowers from 8.05 to 5.57. A further appreciable decrease in pHst is observed only for 3H-CLI at approximately the same ΔpHs value. Taking into consideration the results of our earlier works [4, 24, 31, 32, 35, 36], this decrease in pH of the aqueous suspension may be one of factors promoting formation of the surface palladium–copper composition optimal for realizing catalytic CO oxidation.
Testing Pd(II)–Cu(II)/H-CLI samples as catalysts of the reaction of CO oxidation
Kinetic curves in a \( {\text{C}}_{\text{CO}}^{\text{f}} \)—τ plot obtained as a result of Pd(II)–Cu(II)/H-CLIs testing in the reaction of CO oxidation are shown in Fig. 5. Kinetic and stoichiometric parameters of the reaction in the presence of Pd(II)–Cu(II)/H-CLI catalysts are summarized in Table 6.
Time dependence of \( {\text{C}}_{\text{CO}}^{\text{f}} \) in the course of CO oxidation with air oxygen in the presence of К2PdCl4–Cu(NO3)2–KBr/H–CLI sample at different HNO3 concentrations of 0 (1), 0.25 (2), 0.5 (3), 1.0 (4), and 3.0 (5) used for N-CLI treatment CPd(II) = 2.72 × 10−5, CCu(II) = 5.9 × 10−5, CKBr = 1.02 × 10−4 mol g−1, \( {\text{C}}_{\text{CO}}^{\text{in}} \) = 300 mg m−3, U = 4.2 cm s−1
Table 6 Kinetic and stoichiometric parameters of the reaction of CO oxidation in the presence of K2PdCl4–Cu(NO3)2–KBr/S catalysts (S is N-CLI or H-CLIs)
It should be noted that K2PdCl4–Cu(NO3)2–KBr/N-CLI has a very slight activity at the first minute of the GAM feeding, then, final CO concentrations become even greater and equalize to the initial one in 100 min. All other samples permit CO oxidizing at the steady-state mode down to CO concentrations lower than its maximum permissible concentration, MPCCO, equal to 20 mg m−3 for the working area (Ukrainian Standard). With the increase in \( {\text{C}}_{{{\text{HNO}}_{ 3} }} \), some changes in the kinetics of the initial reaction period relating to the formation of catalytically active sites are observed: the time necessary for the steady-state behavior attainment is shortened, \( {\text{C}}_{\text{CO}}^{\text{f}} \) values at the steady-state mode are lowered, and initial reaction rate (Win) values measured in 5 min of the GAM feeding are heightened. Obviously, the best kinetic parameters are demonstrated by K2PdCl4–Cu(NO3)2–KBr/3H-CLI.
A thermodynamic activity of adsorbed water depended on both the nature of a support and a composition of an active component anchored on it considerably affect kinetic and stoichiometric parameters of the catalytic carbon monoxide oxidation [32]. A thermodynamic activity of water as a component of K2PdCl4–Cu(NO3)2–KBr–H2O/3H-CLI catalyst was varied by changing in its content. For this purpose, catalyst samples air-dried at 110 °C till constant weight and containing 3.1 mmol g−1 of water (Table 3) were hold in desiccators over 30–35% H2SO4 solution for 1, 2, 3 or 4 h, As a result of this holding, the contents of additional water in these samples were 1.66, 2.77, 3.32 or 4.44 mmol g−1, respectively. Water activity values for each sample were determined from the water vapor isotherms (Fig. 4, curve 9) at the total water contents, Σm \( _{{{\text{H}}_{2} {\text{O}}}} \) (Table 7). Figure 6 shows how the thermodynamic activity of water contained in the K2PdCl4–Cu(NO3)2–KBr–H2O/3H-CLI sample affects its activity in the reaction of CO oxidation. Kinetic and stoichiometric parameters of the reaction in the presence of these catalyst samples presented in Table 7 indicate that the increase in \( a_{{{\text{H}}_{2} {\text{O}}}} \) values from 0.26 to 0.87 is accompanied by a very slight decrease (only 2%) in CO conversion values and \( {\text{C}}_{\text{CO}}^{\text{f}} \) values remain under MPCCO.
Table 7 Kinetic and stoichiometric parameters of the reaction of CO oxidation with air oxygen in the presence of K2PdCl4–Cu(NO3)2–KBr–H2O/3H-CLI samples at different contents of adsorbed water (thermodynamic activities of water)
Time dependence of \( {\text{C}}_{\text{CO}}^{\text{f}} \) in the course of CO oxidation with air oxygen at different thermodynamic activities of water contained in К2PdCl4–Cu(NO3)2–KBr/3H–CLI samples \( a_{{{\text{H}}_{2} {\text{O}}}} \): 0.26 (1), 0.79 (2), 0.87 (3), 0.93 (4), 1.0 (5). CPd(II) = 2.72 × 10−5, CCu(II) = 5.9 × 10−5, CKBr = 1.02 × 10−4 mol g−1, \( {\text{C}}_{\text{CO}}^{\text{in}} \) = 300 mg m−3, U = 4.2 cm s−1
As in the case of \( {\text{C}}_{{{\text{HNO}}_{ 3} }} \) varying (Fig. 5), the \( a_{{{\text{H}}_{2} {\text{O}}}} \) varying causes the most appreciable changes in the kinetics of the initial reaction period relating to the formation of catalytically active palladium–copper complexes. Besides the steady-state mode of the reaction proceeding, the catalytic nature of the process is confirmed by the fact that the stoichiometric coefficients of the reaction, n, are more than 1 (Tables 6, 7) indicating a multiple participation of palladium(II) in the process.
Thus, the best catalytic behavior in the reaction of CO oxidation is demonstrated by the palladium–copper catalyst based on acid-modified clinoptilolite obtained as a result of half-hour boiling in 3 M HNO3.
Acid modified forms of clinoptilolite prepared by acid–thermal treatment of natural clinoptilolite with 0.25, 0.5, 1.0, and 3 M HNO3 were used as supports for a palladium–copper composition to obtain samples catalytically active in the reaction of carbon monoxide oxidation. The comparative study of natural and chemically modified samples was performed using XRD and FTIR spectroscopic methods, pH-metry, thermogravimetric analysis, and water vapor adsorption. Spectroscopic methods demonstrated that the maximum degree of natural clinoptilolite dealumination without damage of aluminosilicate framework was attained in the case of 3 M HNO3 treatment (3H-CLI). pH-metry showed that the highest surface acidity was achieved also in the case of 3H-CLI, promoting formation of active anchored palladium–copper complexes. The isotherms of water vapor ad/desorption suggested that the highest specific surface area was, again, obtained for 3H-CLI and K2PdCl4–Cu(NO3)2–KBr-H2O/3H-CLI samples. It should be noted that there was no change in XRD, FTIR, and pH-metry parameters after anchoring Pd(II) and Cu(II) on 3H-CLI. Also, thermogravimetric analysis demonstrated that the residual water adsorption value in K2PdCl4–Cu(NO3)2–KBr–H2O/3H-CLI after its air-drying at 110 °C (the temperature used in our procedure of catalyst preparation) was 3.1 mmol g−1, and this value, according to the water vapor isotherm, corresponded to \( a_{{{\text{H}}_{2} {\text{O}}}} \) = 0.26 (i.e. relative humidity, RH, of 26%). Notably, this catalyst composition was the most active in CO oxidation. Testing CO oxidation at increasing RH showed that the catalyst retained almost all of its activity at RH increasing up to 87%. Thus, this catalytic composition can purify air from carbon monoxide in a steady-state mode down to MPCCO at a wide range of RH and, therefore, can be used in respirators protecting against CO.
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TLR concept and general direction of the study. TAK planning an experiment and discussion of its results. KOG experimental studies, evaluation of the results obtained and their discussion with other authors. AAE providing experimental data concerning water vapor ad/desorption. VYV discussion of some results obtained. All authors read and approved the final manuscript.
All data and materials are presented and described in the text of manuscript.
All authors agree for publish.
Department of Inorganic Chemistry and Chemical Ecology, Odessa I.I. Mechnikov National University, 2, Dvoryanskaya St., Odessa, 65082, Ukraine
Tatyana L. Rakitskaya, Tatyana A. Kiose, Kristina O. Golubchik & Vitalia Y. Volkova
Physicochemical Institute of Environment and Human Protection, 3, Preobrazhenskaya St., Odessa, 65082, Ukraine
Kristina O. Golubchik & Alim A. Ennan
Tatyana L. Rakitskaya
Tatyana A. Kiose
Kristina O. Golubchik
Alim A. Ennan
Vitalia Y. Volkova
Correspondence to Tatyana L. Rakitskaya.
Rakitskaya, T.L., Kiose, T.A., Golubchik, K.O. et al. Acid-modified clinoptilolite as a support for palladium–copper complexes catalyzing carbon monoxide oxidation with air oxygen. Chemistry Central Journal 11, 28 (2017). https://doi.org/10.1186/s13065-017-0256-6
Clinoptilolite
Acid modification
FT-IR spectroscopy
XRD method
Water vapor adsorption
DTG/DTA
Palladium–copper catalysts
CO oxidation


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Australia's leader apologizes for vacation amid wildfires
SYDNEY (AP) — Australian Prime Minister Scott Morrison apologized Sunday for taking a family vacation in Hawaii as deadly bushfires raged across several states, destroying homes and claiming the lives of two volunteer firefighters.
Morrison cut short a vacation with his wife and adult children amid public anger at his absence during a national crisis, and arrived home Saturday night. He spoke to reporters Sunday morning while visiting the headquarters of the Rural Fire Service in Sydney.
"If you had your time over again and you had the benefit of hindsight, we would have made different decisions," Morrison said. "I am sure Australians are fair-minded and understand that when you make a promise to your kids you try and keep it."
"But as prime minister, you have other responsibilities, and I accept that and I accept the criticism," he added.
Morrison said this was not a time for political point-scoring, but a "time to be kind to each other." He said that while he is not a trained firefighter, "I'm comforted by the fact that Australians would like me to be here just simply so I can be here, alongside them, as they are going through this terrible time."
Morrison also answered critics who say his government has not done enough to fight climate change, which has been cited as a major factor in the spate of fires burning across the states of New South Wales, Victoria and South Australia. He said there were also "many other factors" responsible for the unprecedented number of fires during a record-breaking heat wave.
"There is no argument ... about the links between broader issues of global climate change and weather events around the world," he said. "But I'm sure people equally would acknowledge that the direct connection to any single fire event — it's not a credible suggestion to make that link."
Rural Fire Service Commissioner Shane Fizsimmons described Saturday as an "awful day" for firefighters as strong southerly winds fanned more than 100 fires in New South Wales alone.
Dozens of homes have been lost since Thursday in massive wildfires, including the Gospers Mountain blaze, which covered more than 460,000 hectares (1.1 million acres).
Thirty firefighters from Canada and nine from the United States were among fresh crews set to join the battle against the fires on Sunday.
Associated Press writer Steve McMorran in Wellington, New Zealand, contributed to this report.


Since the Feather 32u4 uses an ATmega32u4 chip running at 8 MHz, you can pretty easily get it working with the Arduino IDE. Many libraries (including the popular ones like NeoPixels and display) work great with the '32u4 and 8 MHz clock speed.
Now that you have added the appropriate URLs to the Arduino IDE preferences, you can open the Boards Manager by navigating to the Tools->Board menu.
Once the Board Manager opens, click on the category drop down menu on the top left hand side of the window and select Contributed. You will then be able to select and install the boards supplied by the URLs added to the prefrences. In the example below, we are installing support for Adafruit AVR Boards, but the same applies to all boards installed with the Board Manager.
Next, quit and reopen the Arduino IDE to ensure that all of the boards are properly installed. You should now be able to select and upload to the new boards listed in the Tools->Board menu.
Now you can upload your first blink sketch!
Plug in the Feather 32u4 and wait for it to be recognized by the OS (just takes a few seconds). It will create a serial/COM port, you can now select it from the dropdown, it'll even be 'indicated' as Feather 32u4!
And click upload! That's it, you will be able to see the LED blink rate change as you adapt the delay() calls.
If you ever get in a 'weird' spot with the bootloader, or you have uploaded code that crashes and doesn't auto-reboot into the bootloader, double-click the RST button to get back into the bootloader. The red LED will pulse, so you know that its in bootloader mode. Do the reset button double-press right as the Arduino IDE says its attempting to upload the sketch, when you see the Yellow Arrow lit and the Uploading... text in the status bar.
Note if you're using Ubuntu 15.04 (or perhaps other more recent Linux distributions) there is an issue with the modem manager service which causes the ATmega32u4 micro to be difficult to program. If you run into errors like "device or resource busy", "bad file descriptor", or "port is busy" when attempting to program then you are hitting this issue.
The fix for this issue is to make sure Adafruit's custom udev rules are applied to your system. One of these rules is made to configure modem manager not to touch the board and will fix the programming difficulty issue. Follow the steps for installing Adafruit's udev rules on this page.
ARDUINO IDE SETUP FEATHER HELP!
This guide was first published on Apr 06, 2016. It was last updated on Apr 06, 2016. This page (Using with Arduino IDE) was last updated on Apr 24, 2019.
Customize your Nintendo Labo Piano with Circuit Playground Express!
Make a fancy, color changing Pixie Dust Bag with Circuit Playground Express!
A full-featured GSM/GPRS module with GPS as well!
Animate your headphones with NeoPixels!


Exactly how does a turbocharger "breath life into your machine"? This page looks at different sections of the turbo and how these function.
In simple terms, a turbocharger comprises of a turbine and a compressor connected by a common shaft supported on a bearing system. The turbocharger converts waste energy into compressed air which it pushes into the engine. This allows the engine to produce more power and torque and improves the overall efficiency of the combustion process.
Enlargement of the swept volume allows for an increase in power output, as more air is available in a larger combustion chamber and thus more fuel can be burnt. This enlargement can be achieved by increasing either the number of cylinders or the volume of each individual cylinder. In general, this results in larger and heavier engines. As for as fuel consumption and emissions are concerned, no significant advantages can be expected.
The turbine stage comprises of two components; the turbine 'wheel' and the collector, commonly referred to as a 'housing'. The turbine wheel can be of radial mixed or axial design. Generally, in turbochargers used on high speed engines the turbines are of radial design. On larger engines such as ship propulsion axial turbines are used.
The exhaust gas is guided into the turbine wheel by the housing. The energy in the exhaust gas turns the turbine. Significant amounts of power can be generated in the region of 50kW on a typical 12 litre diesel engine.
Once the gas has passed through the blades of the wheel it leaves the turbine housing via the exhaust outlet area.
The speed of the engine determines how fast the turbine wheel spins. If the engine is in idle mode the wheel will be spinning but at a minimal speed. As you put your foot on the accelerator the wheel starts spinning faster. As more gas passes through the turbine housing, the faster the turbine wheel rotates.
Compressors are the opposite of turbines. Again the compressor stage comprises of two sections, the impeller or 'wheel' and the 'housing'. The compressor wheel is connected to the turbine by a forged steel shaft. As the compressor wheel spins air enters through an area known as the inducer and is compressed through the blades leaving the exducer at a high velocity. The housing is designed to convert the high velocity, low pressure air stream into a high pressure, low velocity air stream through a process called diffusion.
Air enters the compressor at a temperature equivalent to atmosphere, however it leaves the compressor cover at a temperature up to 200 degrees celsius.
Because the density of the air decreases as it is heated up, even more air can be forced into the engine if the air is cooled after the compressor. This is called intercooling or aftercooling and is achieved either by cooling the charge air with water or air.
The Journal Bearings are a free-floating rotational type. To perform correctly, the journal bearings should float between a film of oil (i.e. between bearing & shaft, and bearing & bearing housing.) The bearing clearances are very small, less than the width as a human hair.
Dirty oil, or blockages in the oil supply holes, can cause serious damage to the turbocharger.
Piston Ring Seals can be found at both ends of the turbocharger. They are designed to keep the exhaust pressure out of the bearing housing, and the air pressure out of the bearing housing.
The surface finish on both Turbine and Compressor end bore must be smooth and score free.
A more effective, though complex, method of turbocharging uses a turbine stage where the swallowing capacity is automatically varied while the engine is running. This permits turbine power to be set to provide just sufficient energy to drive the compressor at the desired boost level wherever the engine is operating.
This is achieved by varying the area of a nozzle, a set of guide vanes that control the flow through the turbine. Conventional designs pivot the vanes to achieve different nozzle areas.
Increased useful engine operating speed range.
The wastegate bypasses exhaust gas around the turbine using a valve in the turbine inlet controlled by compressor outlet pressure. This serves to limit turbocharger speed at high engine speeds and loads. In doing this, it reduces the boost pressure attained at full speed full load.
Wastegate turbochargers are matched to give good performance at low engine speed with the valve closed. This improves transient response, reduces exhaust temperatures and emissions. As engine speed increases, the wastegate valve begins to open at a pre-set boost pressure. This has the effect of increasing the swallowing capacity of the turbine; reducing shaft power and avoiding excess air delivery and rotor overspeed.
Turbine housings are manufactured in various grades of spheroidal graphite iron to deal with thermal fatigue and wheel burst containment. As with the impeller, profile machining to suit turbine blade shape is carefully controlled for optimum performance.
The turbine housing inlet flange acts as the reference point for fixing turbocharger position relative to its installation. It is normally the load bearing interface.
The Turbine Wheel is housed in the turbine casing and is connected to a shaft that in turn rotates the compressor wheel.
Compressor housings are also made in cast aluminium. Various grades are used to suit the application. Both gravity die and sand casting techniques are used. Profile machining to match the developed compressor blade shape is important to achieve performance consistency.
Compressor impellers are produced using a variant of the aluminium investment casting process.
A rubber former is made to replicate the impeller around which a casting mould is created. The rubber former can then be extracted from the mould into which the metal is poured. Accurate blade sections and profiles are important in achieving compressor performance. Back face profile machining optimises impeller stress conditions. Boring to tight tolerance and burnishing assist balancing and fatigue resistance. The impeller is located on the shaft assembly using a threaded nut.
A grey cast iron bearing housing provides locations for a fully floating bearing system for the shaft, turbine and compressor which can rotate at speeds up to 170,000 rev/min. Shell moulding is used to provide positional accuracy of critical features of the housing such as the shaft bearing and seal locations. CNC machinery mills, turns, drills and taps housing faces and connections. The bore is finish honed to meet stringent roundness, straightness and surface finish specifications.
The bearing system has to withstand high temperatures, hot shut down, soot loading in the oil, contaminants, oil additives, dry starts.
Journal bearings are manufactured from specially developed bronze or brass bearing alloys. The manufacturing process is designed to create geometric tolerances and surface finishes to suit very high speed operation.
Hardened steel thrust collars and oil slingers are manufactured to strict tolerances using lapping. End thrust is absorbed in a bronze hydrodynamic thrust bearing located at the compressor end of the shaft assembly. Careful sizing provides adequate load bearing capacity without excessive losses.
A turbocharger acts in a similar way as a supercharger and pressurises the air at the inlet manifold. As the inlet valve in the cylinder opens, a greater mass of air is drawn into the cylinder to be burnt with the fuel. More power is generated at each engine speed.
Unlike the supercharger it does not feed off the power output of the engine. The turbocharger uses the waste energy from the exhaust gas to drive a turbine wheel that is linked to the compressor through a shaft. At high altitudes, there is insufficient oxygen to burn the fuel, resulting in low power and black smoke.
At high altitudes the turbocharger rotates faster to increase delivery of air to the engine to compensate. So a turbocharger maintains power from the engine and produces clean emissions.
Fitting a turbocharger and an air cooler can increase engine power even more. An Intercooler removes the heat of compression between the stages of a compressor whereas an aftercooler reduces the temperature of the air leaving the compressor. Delivering cold air means that there is more oxygen per cylinder (cold air has a higher density than warm air) thus more engine power.
Patent obtained by Dr Alfred J Büchi in Switzerland in 1905, for an arrangement of a reciprocating internal combustion engine, rotary compressor and turbine driven by exhaust gas energy.
Turbochargers with axial turbines used in marine, railcar and large stationary applications.
Major engine producers such as Cummins, Volvo and Scania start experimenting with turbocharged engines for trucks using turbochargers supplied by Elliot and Eberspächer. These early designs were unsuccessful due to the large size of the turbocharger. German engineer, Kurt Beirer produces an innovative compact design that is taken up by Schwitzer Corporation, Indianapolis. In 1954 Cummins offer a range of turbocharged engines, the VT12, six cylinder NT, NRT's and JT's.
Also in 1954, Volvo offered their first turbocharged truck diesel, the TD96AS, rated at 185 bhp compared with the 150 bhp naturally aspirated D96AS.
Pole position at Indianapolis in 1952 won by a car powered by a turbocharged Cummins engine.
The Chevrolet Corvair Monza and the Oldsmobile Jetfire were the first turbo-powered passenger cars, and made their debut on the US market in 1962/63. Despite maximum technical outlay, however, their poor reliability caused them to disappear quickly from the market.
After the first oil crisis in 1973, turbocharging became more acceptable in commercial diesel applications. Until then, the high investment costs of turbocharging were offset only by fuel cost savings, which were minimal. Increasingly stringent emission regulations in the late 80's resulted in an increase in the number of turbocharged truck engines, so that today, virtually every truck engine is turbocharged.
In the 70's, with the turbocharger's entry into motor sports, especially into Formula I racing, the turbocharged passenger car engine became very popular. The word "turbo" became quite fashionable. At that time, almost every automobile manufacturer offered at least one top model equipped with a turbocharged petrol engine. However, this phenomenon disappeared after a few years because although the turbocharged petrol engine was more powerful, it was not economical. Furthermore, the "turbo-lag", the delayed response of the turbochargers, was at that time still relatively large and not accepted by most customers.
The real breakthrough in passenger car turbocharging was achieved in 1978 with the introduction of the first turbocharged diesel engine passenger car in the Mercedes-Benz 300 SD, followed by the VW Golf Turbodiesel in 1981. By means of the turbocharger, the diesel engine passenger car's efficiency could be increased, with almost petrol engine "driveability", and the emissions significantly reduced. Today, the turbocharging of petrol engines is no longer primarily seen from the performance perspective, but is rather viewed as a means of reducing fuel consumption and, consequently, environmental pollution on account of lower carbon dioxide (CO2) emissions. Currently, the primary reason for turbocharging is the use of the exhaust gas energy to reduce fuel consumption and emissions.
These failures can be avoided by regular maintenance. When maintaining the air filter system, for example, care should be taken that no tramp material gets into the turbocharger.


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Now this is a fucking story! And sooooo elegantly written. V.C. Andrews (and this is the real V.C. Andrews, not some second rate ghost-writer, writing? riding her coattails) had enormous talent. Holy crap can she weave a tangled web! This is the story of Audrina Adare a young girl with memories like "swiss cheese." A young girl haunted by the ever-present spectre of her deceased older sister, also named Audrina. This is pure soap opera melodrama and this is Andrews' niche, her expertise. She excels and enchants, and this story has everything you could want. A legless woman? You got it! A creepy house with locked doors and musty rooms full of forgotten secrets? Done! A spinster aunt with a broken heart and a hidden past? Here too! Electro-Shock Therapy? You betcha. Forbidden love? Gang rape? Suicide? A woman in a coma? A sexy, trashy cousin with brittle bones and a chip on her shoulder? Yes, yes, yes, yes and yes! That would be Vera.
Oh Vera, dear dear Vera. You are the embodiment of the girl we love to hate. A girl so prevalent in literature and movies and television and you dear, dear Vera are the archetype. I wish Vera had her own novel!! She is soooo much more interesting than boring, vanilla, milquetoast Audrina. Sure she has her weird memory thing. And those disturbing recurring rape nightmares of hers are peculiar. And ya, every night her father rocks her, against her will, in her dead sister's old rocking chair, but VERA?! Vera drove a man to suicide, Vera can be any age. 12? 20? She can pull it off. She is a master manipulator. She dresses provocatively and says whatever comes to mind. She's fearless and brutal and yet so so vulnerable. You see, she has this brittle bone disease, she's so delicate and fragile that if you bump her or shove her, she will fall and break her leg or her rib, or an arm. She breaks her leg, like 4 times in this book! She's so nasty and desperate and dirty and shameful and AMAZING! Vera ran away to the big city and became a nurse. Vera plotted and planned her revenge on the Adare's from day one. Vera is a force of nature! Vera saved this book. Vera, I love you.
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Books published under the following names - Virginia Andrews, V. Andrews, Virginia C. Andrews & V.C. Endrius. Books since her death ghost written by Andrew Neiderman, but still attributed to the V.C. Andrews name
Virginia Cleo Andrews (born Cleo Virginia Andrews) was born June 6, 1923 in Portsmouth, Virginia. The youngest child and the only daughter of William Henry Andrews, a career navy man who opened a tool-and-die business after retirement, and Lillian Lilnora Parker Andrews, a telephone operator. She spent her happy childhood years in Portsmouth, Virginia, living briefly in Rochester, New York. The Andrews family returned to Portsmouth while Virginia was in high school.
While a teenager, Virginia suffered a tragic accident, falling down the stairs at her school and incurred severe back injuries. Arthritis and a failed spinal surgical procedure forced her to spend most of her life on crutches or in a wheelchair.
Virginia excelled in school and, at fifteen, won a scholarship for writing a parody of Tennyson's Idylls of the King. She proudly earned her diploma from Woodrow Wilson High School in Portsmouth. After graduation, she nurtured her artistic talent by completing a four-year correspondence art course while living at home with her family.
After William Andrews died in the late 1960s, Virginia helped to support herself and her mother through her extremely successful career as a commercial artist, portrait painter, and fashion illustrator.
Frustrated with the lack of creative satisfaction that her work provided, Virginia sought creative release through writing, which she did in secret. In 1972, she completed her first novel, The Gods of the Green Mountain [sic], a science-fantasy story. It was never published. Between 1972 and 1979, she wrote nine novels and twenty short stories, of which only one was published. "I Slept with My Uncle on My Wedding Night", a short fiction piece, was published in a pulp confession magazine.
Promise gleamed over the horizon for Virginia when she submitted a 290,000-word novel, The Obsessed, to a publishing company. She was told that the story had potential, but needed to be trimmed and spiced up a bit. She drafted a new outline in a single night and added "unspeakable things my mother didn't want me to write about." The ninety-eight-page revision was re-titled Flowers in the Attic and she was paid a $7,500 advance. Her new-generation Gothic novel reached the bestseller lists a mere two weeks after its 1979 paperback publication by Pocket Books.
Petals on the Wind, her sequel to Flowers, was published the next year, earning Virginia a $35,000 advance. The second book remained on the New York Times bestseller list for an unbelievable nineteen weeks (Flowers also returned to the list). These first two novels alone sold over seven million copies in only two years. The third novel of the Dollanganger series, If There Be Thorns, was released in 1981, bringing Virginia a $75,000 advance. It reached No. 2 on many bestseller lists within its first two weeks.
Taking a break from the chronicles of Chris and Cathy Dollanganger, Virginia published her one, and only, stand-alone novel, My Sweet Audrina, in 1982. The book welcomed an immediate success, topping the sales figures of her previous novels. Two years later, a fourth Dollanganger novel was released, Seeds of Yesterday. According to the New York Times, Seeds was the best-selling fiction paperback novel of 1984. Also in 1984, V.C. Andrews was named "Professional Woman of the Year" by the city of Norfolk, Virginia.
Upon Andrews's death in 1986, two final novels—Garden of Shadows and Fallen Hearts—were published. These two novels are considered the last to bear the "V.C. Andrews" name and to be almost completely written by A
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