Dettainnebär att du kan prova Kinsta riskfritt i 30 dagar! Om du säger upp din prenumeration efter de första 30 dagarna återbetalar vi fortfarande den oanvända delen av din plans prenumeration. Detta inkluderar både månatliga och årliga planer. Det finns inga långsiktiga avtal på Kinsta; du kan säga upp din prenumeration när som helst. An update on blog submissionsAs of July 12, we're navigating some downtime on our legacy web pages, including both and While most Gamasutra pages and functionality have been migrated to the Game Developer website, this does mean that our blog submission tools, profile editor, and other Gamasutra-hosted links are currently unavailable. We're working to get the above features back up and running, and will update this page with more information as we have it. Thank you for your patience as we work to resolve this. Details on ongoing site issues and a link to contact support can also be found on our Report An Issue page. Updated 8/2/22

Whichof the following is found mainly in Groundwater sources and forms a precipitate when oxidized? a. Hydrogen sulfide b. Methane c. Radon d. Iron. d. Iron. 161. What does the term surface runoff refer to? a. Rainwater that soaks in the ground b. Rain that returns to the atmosphere from the earth's surface c. Surface water that overflows the banks of the rivers

CNNDrug overdoses can be life-threatening, but for two women who accidentally took massive hits of LSD, the experience was life changing - and in a good way. A 46-year-old woman snorted a staggering 550 times the normal recreational dose of LSD and not only survived, but found that the foot pain she had suffered from since her 20s was dramatically reduced. Separately, a 15-year-old girl with bipolar disorder overdosed on 10 times the normal dose of the drug, which she said resulted in a massive improvement in her mental experiences were detailed in case reports published in the Journal of Studies on Alcohol and Drugs last month, along with that of a third woman who accidentally overdosed on LSD during the second week of pregnancy. She ultimately gave birth to a healthy son, now 18, who has not shown any impaired development. While the experiences of these women were exceptional, their stories can help inform the resurgence of research into the use of psychedelic substances for the treatment of conditions such as addiction, post-traumatic stress disorder PTSD, depression and anxiety, the researchers believe."No clinical trial research could be done with dosages this high and there are no publications exploring the positive outcomes of very large dosages of LSD," the authors said. "To understand the effects of extremely high dosages of psychedelics such as LSD, an examination of overdoses in naturalistic settings is required." However, experts stressed that these cases were unique and warned against experimenting with the drug, which is illegal in the US and UK. "They don't really show the benefits of LSD, rather they show that in some people exceptionally high doses don't lead to enduring harms and may do some good," said professor David Nutt, director of the Neuropsychopharmacology Unit in the Division of Brain Sciences at Imperial College London. The details of each case study came from interviews with the individual women, their family members and friends, drug suppliers, witnesses, health records and case notes,according to the LSD for cocaineThe 49-year-old woman, known as CB, had contracted Lyme disease in her early 20s, which damaged her feet and ankles and left her in "significant pain." In September 2015, she took 55 milligrams of what she believed was cocaine but was actually "pure LSD in powder form." The authors defined a normal recreational dose as 100 micrograms - equal to woman blacked out and vomited frequently for the next 12 hours but reported feeling "pleasantly high" for the 12 hours after that - still vomiting, but less often. According to her roommate, she sat mostly still in a chair, either with her eyes open or rolled back, occasionally speaking random words. Ten hours later, she was able to hold a conversation and "seemed coherent."Her foot pain was gone the next day and she stopped using morphine for five days. While the pain returned, she was able to control it with a lower dose of morphine and a microdose of LSD every three days. After more than two years, in January 2018, she stopped using both morphine and LSD and reported no withdrawal symptoms, although the case report said she did experience an increase in anxiety, depression and social case studies were compiled by Mark Haden, executive director of Canada's Multidisciplinary Association for Psychedelic Studies and an adjunct professor at the University of British Colombia School of Population and Public Health, and Birgitta Woods, a psychiatrist in noted that in CB's case "ingestion of 550 times the normal recreational dosage of LSD was not fatal and had positive effects on pain levels and subsequent morphine withdrawal." The authors note in the study that no lethal doses of LSD have been documented, although they said scientists have estimated that a lethal dose in humans would be 14,000 manufactured in Switzerland in 1938 as a potential treatment for bleeding disorders, LSD's scientific name Lysergic acid diethylamid subsequent popularity as a recreational drug saw it criminalized in much of the world. In both the United States and United Kingdom, LSD is a schedule 1 drug, the most restrictive with a 'normal brain'For the 15-year-old who overdosed on 10 times the normal LSD dose at the Summer Solstice party in June 2000, known as AV, the experience led to a dramatic change in her mental health. The girl was diagnosed with bipolar disorder at the age of 15, having suffered from depression and hallucinations from the age of 12, which at times had put her in a hospital, including once after she bit her mother, the case study said. Her overdose happened when the supplier of liquid LSD made a decimal place error when preparing individual hits diluted in glasses of water, making them 1,000 mcg per glass instead of 100mcg. AV drank one glass and leftover drops from two said she behaved erratically for the next hours, followed by what they believed to be a seizure, as she was lying in a fetal position with her arms and fists clenched tightly. An ambulance was called, but by the time the paramedics arrived 10 minutes later she was alert and oriented. When her father visited her in the hospital the next morning, AV told him, "It's over." While he thought his daughter was referring to the LSD overdose, she later clarified that she meant her bipolar illness was cured and she felt able to experience life with a "normal brain."She was free from all mental illness symptoms bipolar or other for 13 years until she gave birth and experienced postpartum depression, the case study the third case detailed in the paper, a 26-year-old woman, referred to as NM, at the same party drank half a glass of the LSD-dosed water and subsequently found out she was pregnant. However, the authors said the overdose "did not negatively affect the course of NM's pregnancy." Nor did it have any other obvious negative developmental effects on her son, now 18. Research renaissanceWhile LSD has long been used for its mind-bending effects, the drug has also been used to treat mental health problems. During the 1940s and early 1950s tens of thousands of patients took LSD and other psychotropics as part of research into their effects on cancer anxiety, alcoholism, opioid use disorder, depression and PTSD. Researchers began to see psychedelics as possible new tools for shortening type of research soon stopped in the 1960s when LSD was declared illegal in the United States. However, in the past decade, research in this area has seen a resurgence, with scientists today exploring the role of hallucinogens on treatment-resistant depression, post traumatic stress disorder, cancer-related anxiety, addictions, and even anorexia. Fears of any permanent damage from psychedelics were eased by a large 2015 study of 130,000 American adults, comparing users to non-users. The study found no link between the use of LSD, mescaline or psilocybin the psychoactive compounds in magic mushrooms and suicidal behavior or mental health some studies have found unpleasant effects from LSD, both during the high and after. People with negative reactions can have difficulty concentrating, dizziness, lack of appetite, dry mouth, nausea and/or imbalance for up to 10 to 14 hours after taking LSD; headaches and exhaustion can last up to 72 Sandee LaMotte contributed to this reportCorrection A previous version of this story misidentified the origin of psilocybin.
イベントレポート セゾン投信とコラボ!. 女性限定マネーセミナーが大好評のうちに終了. 『【女性限定】AB×セゾン投信 特別企画 日比谷の夜景とスパークリングワインを楽しみながら将来のための自分磨きを始めませんか?. 』の開催報告です. 7月9日の19
AbstractThe dynamic back-action caused by electromagnetic forces radiation pressure in optical1,2,3,4,5,6 and microwave7 cavities is of growing interest8. Back-action cooling, for example, is being pursued as a means of achieving the quantum ground state of macroscopic mechanical oscillators. Work in the optical domain has revolved around millimetre- or micrometre-scale structures using the radiation pressure force. By comparison, in microwave devices, low-loss superconducting structures have been used for gradient-force-mediated coupling to a nanomechanical oscillator of picogram mass7. Here we describe measurements of an optical system consisting of a pair of specially patterned nanoscale beams in which optical and mechanical energies are simultaneously localized to a cubic-micron-scale volume, and for which large per-photon optical gradient forces are realized. The resulting scale of the per-photon force and the mass of the structure enable the exploration of cavity optomechanical regimes in which, for example, the mechanical rigidity of the structure is dominantly provided by the internal light field itself. In addition to precision measurement and sensitive force detection9, nano-optomechanics may find application in reconfigurable and tunable photonic systems10, light-based radio-frequency communication11 and the generation of giant optical nonlinearities for wavelength conversion and optical buffering12. Your institute does not have access to this article Relevant articles Open Access articles citing this article. A thermomechanical finite strain shape memory alloy model and its application to bistable actuators Marian Sielenkämper & Stephan Wulfinghoff Acta Mechanica Open Access 06 July 2022 Active optomechanics Deshui Yu & Frank Vollmer Communications Physics Open Access 17 March 2022 Optomechanical crystals for spatial sensing of submicron sized particles D. Navarro-Urrios, E. Kang … G. Fytas Scientific Reports Open Access 09 April 2021 Access options Subscribe to JournalGet full journal access for 1 year185,98 €only 3,65 € per issueAll prices are NET prices. VAT will be added later in the calculation will be finalised during articleGet time limited or full article access on ReadCube.$ prices are NET prices. Additional access options Log in Learn about institutional subscriptions ReferencesArcizet, O., Cohadon, Briant, T., Pinard, M. & Heidmann, A. Radiation-pressure cooling and optomechanical instability of a micromirror. Nature 444, 71–73 2006ADS CAS Article Google Scholar Gigan, S. et al. 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Lett. 96, 103901 2006ADS Article Google Scholar Olson, R. H. & El-Kady, I. Microfabricated phononic crystal devices and applications. Meas. Sci. Technol. 20, 012002 2008ADS Article Google Scholar Download referencesAcknowledgementsThe authors would like to thank Q. Lin for extensive discussions regarding this work, and for pointing out the origin of the mechanical resonance interference. Funding for this work was provided by a US Defense Advanced Research Projects Agency seedling effort managed by H. Temkin, and through an Emerging Models and Technologies grant from the US National Science Contributions and performed the majority of the fabrication and testing of devices and performed the optical and mechanical simulations. along with and developed the device concept. and all contributed to planning the measurements. All authors worked together to write the informationAuthors and Affiliations Thomas J. Watson, Sr. Laboratory of Applied Physics, California Institute of Technology, Pasadena, California 91125, USA , Matt Eichenfield, Ryan Camacho, Jasper Chan, Kerry J. Vahala & Oskar PainterAuthorsMatt EichenfieldYou can also search for this author in PubMed Google ScholarRyan CamachoYou can also search for this author in PubMed Google ScholarJasper ChanYou can also search for this author in PubMed Google ScholarKerry J. VahalaYou can also search for this author in PubMed Google ScholarOskar PainterYou can also search for this author in PubMed Google ScholarCorresponding authorCorrespondence to Oskar informationSupplementary InformationThis file contains Supplementary Data, Supplementary Methods, Supplementary Figures S-1-S-3 with Legends and Supplementary References. PDF 558 kbPowerPoint slidesRights and permissionsAbout this articleCite this articleEichenfield, M., Camacho, R., Chan, J. et al. A picogram- and nanometre-scale photonic-crystal optomechanical cavity. Nature 459, 550–555 2009. citationReceived 15 December 2008Accepted 08 April 2009Published 13 May 2009Issue Date 28 May 2009DOI Further reading Active optomechanics Deshui Yu Frank Vollmer Communications Physics 2022 Optomechanical ratchet resonators Wenjie Nie Leqi Wang Yueheng Lan Science China Physics, Mechanics & Astronomy 2022 A thermomechanical finite strain shape memory alloy model and its application to bistable actuators Marian Sielenkämper Stephan Wulfinghoff Acta Mechanica 2022 Axial magnetic field effect on wave propagation in bi-layer FG graphene platelet-reinforced nanobeams Ashraf M. Zenkour Mohammed Sobhy Engineering with Computers 2022 Optomechanical crystals for spatial sensing of submicron sized particles D. Navarro-Urrios E. Kang G. Fytas Scientific Reports 2021 CommentsBy submitting a comment you agree to abide by our Terms and Community Guidelines. If you find something abusive or that does not comply with our terms or guidelines please flag it as inappropriate.
solutionsmanual fundamentals of modern manufacturing: materials, processes, and systems second edition New 24 Apr 2019 1 Mail not sending! Eventually decided to retire’ my tried, trusted and tested 11-year-old XP computer and dive into Windows-10...for general use😉 Struggling just a tad with the not so subtle differences between XP and W10 especially with the email element! Old habits die hard... I have created the 'people' name and e-mail address details and tried to send a mail to my full contact list 18 contacts as 'bcc' but the result was an incoming message as follows..."We weren't able to send this message, so we've put it in your Drafts folder. Before you try sending it again, you can check to see if the address is correct and that no attachments are too large." There was no attachment... just a few lines of I have to select a specific address in the To box? With my previous OutlookExpress in XP I was able to send as an entire 'bcc' . Any advice would be appreciated, New 24 Apr 2019 2 Hi, which mail program are you using? It does take a little while to create an account in an email client, assuming that's what you are using. A screenshot or so might help. Not that the Mail client in Windows is more limited than OE was. I gave up on MS email offerings after OE was dropped, the Win Mail... New 24 Apr 2019 3 Thanks for your input... I am using the 'default' Mail programme as shown in the W10 task bar. Incoming mails are OK! New 24 Apr 2019 4 Hi, I don't use Mail, so hopefully someone who has this configured may reply. Note too that you can't back up or bulk export emails stored by Mail. You might find this interesting ref. bcc, as it both indicates you can send solely bcc, but indicates other related issues win 10 mail not showing BCC of my sent emails - Microsoft Community Of course there are continual updates, so the issue mentioned there may have been resolved by MS. To me it points back to this being a limited client. New 24 Apr 2019 5 At a guess the Windows 10 Mail App and the linked People App are being used. Rather similar arrangement to Outlook Express and the Windows Address Book of Windows XP. You have probably fallen foul of increased security by trying to send bulk Emails to 18 contacts at the same time. This could be due to the Email providers measures against Spammers, or limitations in the Mail App. A simple mailing experiment might sort out which it is. You may have to go to whoever is your Email provider by the Webmail method and consult their Help pages on the subject. Windows 10 Mail App is limited as a Mail client, for bulk Emails something like MS Outlook the desktop application would be more suited. New 25 Apr 2019 6 Helmut said At a guess the Windows 10 Mail App and the linked People App are being used. Rather similar arrangement to Outlook Express and the Windows Address Book of Windows XP. You have probably fallen foul of increased security by trying to send bulk Emails to 18 contacts at the same time. This could be due to the Email providers measures against Spammers, or limitations in the Mail App. A simple mailing experiment might sort out which it is. You may have to go to whoever is your Email provider by the Webmail method and consult their Help pages on the subject. Windows 10 Mail App is limited as a Mail client, for bulk Emails something like MS Outlook the desktop application would be more suited. I guess you could be correct, Helmut, regarding the 'security' issues over 'bulk' postings! Five appears to be the best/highest number at this time! I have just downloaded 'Mailbird' ~~~ from the reviews and other information obtained it would appear to be a good alternative and it is 'outside' the tentacles of MS!!! Thanks for your - - Updated - - - Installed 'Mailbird' but have the same issues! Can receive mails from each of three accounts but cannot send through any of them! see message belowDelivery to the following recipients was aborted after 0 seconds* d***b*** I have purposely amended this address for obvious reasons!.Reason The following message to [email protected] was reason for the problem 550 Requested action not taken mailbox unavailable. [ I setup the e-accounts through W10 and assumed they would be correct ~~~ but can't find access to check if I have pop-3 or IMAP settings. My redundant PC was running XP with pop-3/smpt correct? settings. Don't even know if this would matter and I am waiting on a response from my ISP yawn... New 25 Apr 2019 7 Normally your ISP provides all the details necessary for your account. Try Google example- my ISP is Talktalk. Search for Talktalk email client settings and see TalkTalk Mail Settings TalkTalk IMAP and SMTP Settings - Email Settings Guide as an early result Example Thunderbird After entering the email address, Thunderbird spent a minute trying to get appropriate configurations details automatically. Then note the choice of IMAP of POP3 it offers - that's your decision. New 25 Apr 2019 8 settings? - where? Thanks for your input ~~~ I am becoming more convinced this issue is in the 'smtp' area... Daft question, then...how to access these settings in W10? I could easily access them in XP but even a 'search' does not bring up anything to do with mail settings Fortunately my incoming posts are not affected. I have been with 'Tiscali' for many years and do not relish having to advise a huge number of people and organisations of a change to, say, 'TalkTalk'... Just point me to the hide-out for mail settings, please! Ken New 25 Apr 2019 10 misunderstanding... Sorry - maybe I did not explain sufficiently... Where/how do I access the actual settings in W10 for the mail client. XP seems so simple having moved 'up' to W10 - nothing is where I used to find it...- - - Updated - - - OK ~~~ I found the 'settings' for mail cunningly hidden in 'settings' and clicked on the mail icon then ferreted about to see what I was searching for... Unfortunately, the settings in the IMAP are exactly correct so I am now wondering - should I change to the 'pop' variant which I used in my XP machine without any challenges at all? I think I must be the person the "*** for Dummies" were written
袋田の住職山寺日記. 大好き!. いばらき ブログトップ. 海浜公園のコキアの紅葉が始まっています [大好き!. いばらき] 10月3日、今朝は、第一日曜日ということで月例坐禅会でした。. 朝は、寒いぐらいですが、日中は気温が上がり、30℃の残暑が続いて
If you want to use Docker on servers or virtual machines, technical limitations can sometimes lead to a situation in which – even without intentional limitation – it is not possible to access the outer world from a docker container. Docker MTU configuration A common problem when operating dockers within a virtualization infrastructure is that the network cards provided to virtual machines do not have the default MTU of 1500. This is often the case, for example, when working in a cloud infrastructure OpenStack. The Docker Daemon does not check the MTU of the outgoing connection at startup. Therefore, the value of the Docker MTU is set to 1500. Detecting the problem With the command ip link you can display the locally configured network cards and their MTU 1 lo mtu 65536 qdisc noqueue state UNKNOWN mode DEFAULT group default qlen 1000 link/loopback 000000000000 brd 000000000000 2 ens3 mtu 1454 qdisc fq_codel state UP mode DEFAULT group default qlen 1000 link/ether aabbccddeeff brd ffffffffffff 3 docker0 mtu 1500 qdisc noqueue state DOWN mode DEFAULT group default link/ether uuvvwwxxyyzz brd ffffffffffff If the outgoing interface in this case ens3 has an MTU smaller than 1500, some action is required. If it is greater than or equal to 1500, this problem does not apply to you. Solving the problem docker daemon To solve the problem, you need to configure the Docker daemon in such a way that the virtual network card of newly created containers gets an MTU that is smaller than or equal to that of the outgoing network card. For this purpose create the file /etc/docker/ with the following content { "mtu" 1454 } In this example, I chose 1454 as the value, as this corresponds to the value of the outgoing network card ens3. After restarting the Docker daemon, the MTU of new containers should be adapted accordingly. However, docker-compose create a new bridge network for every docker-compose environment by default. Solving the problem docker-compose If you work with docker-compose, you will notice that in containers created by docker-compose, the MTU of the daemon is not inherited. This happens because the mtu entry in /etc/docker/ file only affects the default bridge. Therefore you have to specify the MTU explicitly in the for the newly created network ... networks default driver bridge driver_opts 1454 After rebuilding the docker-compose environment docker-compose down; docker-compose up, the containers should use the modified MTU. I personally don’t like this solution, because the docker-compose files have to be specially adapted to their environment and therefore lose their portability. Unfortunately, I am not aware of any other solution to this problem at the moment. Page8 The Moorabool News – 2 August, 2022. News. Email - news@themooraboolnews.com.au. Power outages of concern By Lachlan Ellis Powercor has responded to the community’s concerns, after a Home Collaboration Microsoft Exchange Posted by Kyle_Stoker I have one company who is trying to email us and they keep getting this error when they send us a email. Any help would be appreciated! 550 Message rejected because SPF check failed check Best Answer checkBest Answer Type their domain in to this tool an SPF record checker and see if it passes. If not, the problem is on their end..... an invalid SPF record means it could be spam / or a forged address and it seems reasonable to me to reject such messages. TL;DR It's their problem, tell them to fix their SPF record. The alternative makes YOU less secure. 1 found this helpful thumb_up thumb_down View Best Answer in replies below 26 Replies mhache This person is a verified professional. Verify your account to enable IT peers to see that you are a professional. cayenne Check with this if you have a proper SPF record. If not, fix it and emails should come through fine. 1 found this helpful thumb_up thumb_down checkBest Answer Type their domain in to this tool an SPF record checker and see if it passes. If not, the problem is on their end..... an invalid SPF record means it could be spam / or a forged address and it seems reasonable to me to reject such messages. TL;DR It's their problem, tell them to fix their SPF record. The alternative makes YOU less secure. 1 found this helpful thumb_up thumb_down THash This person is a verified professional. Verify your account to enable IT peers to see that you are a professional. serrano I would recommend using the Exchange Connectivity Tester on your domain to see if it reports any problems. Also do you have an existing SPF record for your domain? If not you'll need to work with your DNS provider and get one implemented. Here is a good wizard for creating SPF records Microsoft SPF Sender ID Framework Wizard Was this post helpful? thumb_up thumb_down Your error seems to indicate their mail isn't passing SPF and getting rejected. Either disable SPF checking or ask them to fix their SPF records Was this post helpful? thumb_up thumb_down Did I misunderstand? From what the OP says, it is a company trying to email him... meaning it isn't his SPF record but the other companies. Was this post helpful? thumb_up thumb_down Thats correct Kelly we are able to email their company and the mail will go through but when they email us the mail is rejected from our server. I did a SPF check on their domain name and it does look like it passes through the MXtoolbox check. I did the same with ours and it came back with No spf records found. Was this post helpful? thumb_up thumb_down Kyle5862 wrote Thats correct Kelly we are able to email their company and the mail will go through but when they email us the mail is rejected from our server. I did a SPF check on their domain name and it does look like it passes through the MXtoolbox check. I did the same with ours and it came back with No spf records found. I suspect they may either be routing through a Smarthost,or somewhere the mail is getting scooped up and redirected. Either way the SPF record they don't have doesn't match the address the mail is coming from For interest sake you could compare the server IP from the mail headers with their SPF and confirm this - but it really isn't your fault or problem Was this post helpful? thumb_up thumb_down mhache This person is a verified professional. Verify your account to enable IT peers to see that you are a professional. cayenne Kyle5862 wrote Thats correct Kelly we are able to email their company and the mail will go through but when they email us the mail is rejected from our server. I did a SPF check on their domain name and it does look like it passes through the MXtoolbox check. I did the same with ours and it came back with No spf records found. Whether this is the cause of the problem or not you should really set up an SPF record. Was this post helpful? thumb_up thumb_down Seems like the issue would be on their end and I agree that we should have an SPF record setup. Im new to this organization so still working out some bugs. Thanks everyone for the help! Was this post helpful? thumb_up thumb_down Because you don't have this trouble with other inbound email, I suspect the problem is totally on their end. They probably have a mailserver that this sender is relaying through, and it doesn't like the IP the customer is at. Hard to tell. Inbound though, couldn't you just whitelist their domain and skip the SPF as a result? A white list should override anything but AV checks. Was this post helpful? thumb_up thumb_down mhache This person is a verified professional. Verify your account to enable IT peers to see that you are a professional. cayenne David1618 wrote Because you don't have this trouble with other inbound email, I suspect the problem is totally on their end. They probably have a mailserver that this sender is relaying through, and it doesn't like the IP the customer is at. Hard to tell. Inbound though, couldn't you just whitelist their domain and skip the SPF as a result? A white list should override anything but AV checks. If you whitelist a domain you also whitelist that domain if it's spoofed. SPF records prevent spoofed emails from coming in. In the long run you're better off just setting up a proper SPF record and then creating a detailed layout of why it's the far end problem. That way they'll be more likely to send it to their IT staff to correct. Was this post helpful? thumb_up thumb_down Sorry for the questions but where would I be able to whitelist there domain in the Exchange management console. I am new to exchange so I am still learning where to do a lot of the features. My plan is to whitelist there domain temporarily so we can get the drawings we need then work with their IT to resolve the issue. Thanks! Was this post helpful? thumb_up thumb_down You can pass a test I've done this personally with a "false positive" of sorts..... Imagine a scenario where email could originate from 5 different mail servers. You test once, the SPF record happens to include the mail server it is sent from THAT TIME, and therefore it's a valid SPF record. Then on attempt/test 2 it uses a different mail server, not accounted for in the SPF record, and subsequently fails. It's possible to have a partially working SPF record. One that will pass tests sometimes and not others. It's happened to me Was this post helpful? thumb_up thumb_down mhache wrote David1618 wrote Because you don't have this trouble with other inbound email, I suspect the problem is totally on their end. They probably have a mailserver that this sender is relaying through, and it doesn't like the IP the customer is at. Hard to tell. Inbound though, couldn't you just whitelist their domain and skip the SPF as a result? A white list should override anything but AV checks. If you whitelist a domain you also whitelist that domain if it's spoofed. SPF records prevent spoofed emails from coming in. In the long run you're better off just setting up a proper SPF record and then creating a detailed layout of why it's the far end problem. That way they'll be more likely to send it to their IT staff to correct. I don't understand why you keep telling him to set up an SPF record.... While a good practice, it's completely irrelevant to him receiving email..... and has nothing to do with the problem posted. His email is not being bounced, the senders is being bounced. Was this post helpful? thumb_up thumb_down Kelly Armitage wrote You can pass a test I've done this personally with a "false positive" of sorts..... Imagine a scenario where email could originate from 5 different mail servers. You test once, the SPF record happens to include the mail server it is sent from THAT TIME, and therefore it's a valid SPF record. Then on attempt/test 2 it uses a different mail server, not accounted for in the SPF record, and subsequently fails. It's possible to have a partially working SPF record. One that will pass tests sometimes and not others. It's happened to me Not sure what you mean, but an SPF record should include ALL mail servers you're sending email from for your domain. That way the SPF record ALWAYS passes. It should never pass sometimes, but not at other times. Was this post helpful? thumb_up thumb_down Oliver Kinne wrote Kelly Armitage wrote You can pass a test I've done this personally with a "false positive" of sorts..... Imagine a scenario where email could originate from 5 different mail servers. You test once, the SPF record happens to include the mail server it is sent from THAT TIME, and therefore it's a valid SPF record. Then on attempt/test 2 it uses a different mail server, not accounted for in the SPF record, and subsequently fails. It's possible to have a partially working SPF record. One that will pass tests sometimes and not others. It's happened to me Not sure what you mean, but an SPF record should include ALL mail servers you're sending email from for your domain. That way the SPF record ALWAYS passes. It should never pass sometimes, but not at other times. Yup it definitely *SHOULD* but a misconfigured one can pass on some occasions and fail on others.... which it would seem to make sense in this case based on the fact that mxtoolbox is saying the SPF is valid, and Exchange is bouncing it based on an invalid SPF.... So I mean exactly what I said...... Was this post helpful? thumb_up thumb_down Kelly Armitage wrote Yup it definitely *SHOULD* but a misconfigured one can pass on some occasions and fail on others.... which it would seem to make sense in this case based on the fact that mxtoolbox is saying the SPF is valid, and Exchange is bouncing it based on an invalid SPF.... So I mean exactly what I said...... The way I read "550 Message rejected because SPF check failed", it means the SPF record doesn't include the mail server that the email is sent from. I don't think the SPF record itself is malformed - as you say MXToolBox confirms it's valid. So if it's a real problem, just whitelist the sending mail server, so that it doesn't check for SPF. Not sure how to do that in Exchange, but I'd think it should be possible. Was this post helpful? thumb_up thumb_down However, of course, if you can ask the sending company to add the IP address of the sending server to their SPF record, that would be even better, but in my experience you might as well hit your head on a brick wall... ; Was this post helpful? thumb_up thumb_down That is specifically what SPF tests check for..... Oliver Kinne wrote Kelly Armitage wrote Yup it definitely *SHOULD* but a misconfigured one can pass on some occasions and fail on others.... which it would seem to make sense in this case based on the fact that mxtoolbox is saying the SPF is valid, and Exchange is bouncing it based on an invalid SPF.... So I mean exactly what I said...... The way I read "550 Message rejected because SPF check failed", it means the SPF record doesn't include the mail server that the email is sent from. I don't think the SPF record itself is malformed - as you say MXToolBox confirms it's valid. So if it's a real problem, just whitelist the sending mail server, so that it doesn't check for SPF. Not sure how to do that in Exchange, but I'd think it should be possible. If you white-list the domain as said above then you're defeating the purpose of checking for them at all... I agree... the people sending the mail do not have a properly configured read ALL INCLUSIVE SPF record.... Was this post helpful? thumb_up thumb_down No, I'm not saying whitelist the domain. Just whitelist the IP of the sending server. Was this post helpful? thumb_up thumb_down Not a bad idea if he can determine the IP from one of the bounced messages..... Was this post helpful? thumb_up thumb_down I won't whitelist people who fail SPF checks because assuming DNS is working all down the line we're basically doing what they say we should do. I'd do a manual lookup of the txt record from your end and see if it matches what you get from MX Toolbox. Was this post helpful? thumb_up thumb_down Thanks everyone for the help with this I really appreciate it I have contacted their IT and let them know the issue is on their end and they are looking into it. I have also began the process of setting up a SPF record for our company. Appreciate all the tips! 1 found this helpful thumb_up thumb_down mhache wrote David1618 wrote Because you don't have this trouble with other inbound email, I suspect the problem is totally on their end. They probably have a mailserver that this sender is relaying through, and it doesn't like the IP the customer is at. Hard to tell. Inbound though, couldn't you just whitelist their domain and skip the SPF as a result? A white list should override anything but AV checks. If you whitelist a domain you also whitelist that domain if it's spoofed. SPF records prevent spoofed emails from coming in. In the long run you're better off just setting up a proper SPF record and then creating a detailed layout of why it's the far end problem. That way they'll be more likely to send it to their IT staff to correct. I wasn't saying it was the optimal way to configure, just how I would workaround until the sender got their system working right. I've not caught up since my last posting, but I still believe this to be a sender's issue Was this post helpful? thumb_up thumb_down How to whitelist or disable SPF depends on the Exchange version,steps for either method can be found here Was this post helpful? thumb_up thumb_down Hi...Even we are facing same domain has valid SPF record. But still mails are bouncing with error as "SPF FROM check failed" Was this post helpful? thumb_up thumb_down Read these next... Spark! Pro Series - 16 August 2022Spiceworks Originals Today in History 16 August 1501 – Michelangelo awarded contract to create his statue of David at Florence Cathedral by the Overseers of the Office of Works The Operai of the Duomo 1691 – Yorktown, Virginia f... Weather proof box to house a 5 port ethernet switchNetworkingI am doing a project for a non-profit museum and part of that is finding a way to mount 2 5 port ethernet POE switches 2 different locations on a pole. This will have to be done in a small weather proof lockable box/cabinet. Basically, I am going to be ...Snap! UK water supply, Android 13, Zoom for Mac, Artemis I, cable closet storySpiceworks OriginalsYour daily dose of tech news, in brief. Welcome to Tuesday, August 16th, which is also Tell A Joke Day. I imagine most of you know the common UDP joke so I'll go with another one. What wedding gift should you buy for a Windows administrator? I don'...Patch cabinet spaghettiNetworkingI’m awaiting the arrival of new switches. 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Journal List Wiley-Blackwell Online Open PMC4499260 Angew Chem Int Ed Engl. 2014 Aug 25; 5335 9251–9256. Jesper J H B Sattler, Ines D Gonzalez-Jimenez, Lin Luo,* Brien A Stears, Andrzej Malek, David G Barton, Beata A Kilos, Mark P Kaminsky, Tiny W G M Verhoeven, Eline J Koers, Marc Baldus, and Bert M Weckhuysen*AbstractA novel catalyst material for the selective dehydrogenation of propane is presented. The catalyst consists of 1000 ppm Pt, 3 wt % Ga, and wt % K supported on alumina. We observed a synergy between Ga and Pt, resulting in a highly active and stable catalyst. Additionally, we propose a bifunctional active phase, in which coordinately unsaturated Ga3+ species are the active species and where Pt functions as a gallium oxide, heterogeneous catalysis, platinum, propane dehydrogenation, synergistic effectsThe recent exploration and production of hydrocarbons from shale basins in the USA such as in Barnett, Marcellus, Haynesville, and Eagle Ford, has led to a rebound in its energy competitiveness. Currently, the USA is at the lowest level of crude oil imports in 25 years.[1] While oil production has greatly increased in these shale plays, natural gas has increased even more significantly, with the Energy Information Agency projecting that by 2040, 50 % of the natural gas production within the USA will come from shale.[2] This new source of hydrocarbons has the potential to impact the worldwide supply of natural gas, because shale formations are found throughout the world. A recent study estimates that there are 207 trillion cubic meters of technically recoverable shale gas globally. China is estimated to have the world’s largest reserves in shale at 32 trillion cubic meters.[3] Although most shale gas outside of the USA is not currently produced, it is reasonable to expect that these low-cost feedstocks for chemicals and fuels production will become available worldwide. These developments will without a doubt impose significant technical and economic challenges and opportunities on the chemical industry as a substantial amounts of heavier paraffins, such as propane are obtained from shale gas deposits, there is a vast and growing interest in utilizing propane dehydrogenation PDH technologies for the on purpose production of propene.[4] Within this context, it is important to mention that there have been five newly announced PDH units in the USA, while 9 to 17 PDH units may be built in China.[5] The majority of these projects is based on one of the two primary existing technologies for PDH; the Oleflex process from UOP and the CATOFIN process from CB&I Lummus.[6] Although substantial improvements in catalyst materials Pt-Sn/Al2O3 for Oleflex and Cr/Al2O3 for CATOFIN and process conditions have been made for both technologies, challenges related to their activity, stability, and selectivity still have to be we present a new family of very stable, active, and selective catalyst materials for the dehydrogenation of propane to propene based on Pt–Ga/Al2O3. A few papers have already been published, in which Pt and Ga were combined to produce PDH catalysts, but in these systems Ga is deemed to function as a promoter element, with Pt being the active dehydrogenation element.[7] This is in contrast with our current catalyst, in which Pt is present in minute amounts and Ga is the active dehydrogenation element. A clear synergistic effect is observed between both components, which results in a very stable catalyst material that is highly resistant to deactivation, by perform a systematic study, a series of nine catalyst materials was prepared by depositing 1000 ppm Pt, or 3 wt % Ga, and wt % K on an alumina support. Details of the catalyst characterization X-ray diffraction XRD, transmission electron microscopy energy-dispersive X-ray spectroscopy TEM-EDX, and N2-physisorption are given in the Supporting Information Figures S1 and S2, and Table S1. From these characterization data it is concluded that all the compounds are homogeneously and highly dispersed on the catalyst materials as there is no evidence for the presence of crystalline catalytic performance of the prepared materials has been tested in a lab-scale reactor for eight successive dehydrogenation–regeneration cycles. Each cycle consists of a 15 min PDH step at 620 °C, followed by a treatment in air at 750 °C for 30 min. The reactor is flushed with He between these steps. The resultant gas stream is analyzed by gas chromatography as described in the Supporting Information Figure S3. The setup also allows for the use of operando Raman and UV/Vis spectroscopy to track the deposition of coke on the catalyst materials.[8] A complete list of the catalysts prepared and their respective activity and selectivity data for the first, second, and eighth PDH cycle is summarized in Table 1. Additionally, Figure 1 shows a comparison between the conversion and selectivity obtained during the first eight cycles for the bare Al2O3 support, Pt, 3Ga, Pt3Ga, and Pt3GaK catalyst of propane X, green and selectivity S, blue for propene during PDH on the Al2O3 support, Pt, 3Ga, Pt3Ga, and Pt3GaK catalysts for each of the eight successive dehydrogenation cycles. The exact values of X and S for the first, second, and eighth cycle are summarized in Table 1. Evidently, both Pt and Ga are required to obtain a highly active selective and stable propane dehydrogenation 1The conversion X and selectivity S obtained halfway through the first, second, and eighth cycle of the ten catalyst materials under investigation.[a]Catalyst material supported on Al2O3CodeFirst cycleSecond cycleEighth cycleCoke dep[b]Darkening[c]D/G[d]X [%]S [%]X [%]S [%]X [%]S [%]wt %[%]−1000 ppm Pt, wt % Ga, wt % ppm Pt, 3 wt % Ga, wt % ppm Pt, wt % ppm Pt, 3 wt % wt % Ga, wt % wt % Ga, wt % wt % wt % ppm Table 1 and Figure 1, it can be concluded that the catalytic conversion varies strongly between the different catalyst materials. In case of the catalysts containing both Pt and Ga, this value is close to the equilibrium conversion which is ca. 55 % at 620 °C and 1 atm pressure for the first dehydrogenation cycle. When Pt is absent, the conversion is roughly halved, while the absence of Ga results in an even greater drop in conversion. At the same time, the selectivity is high for all catalysts containing both Pt and Ga, but decreases for the materials containing only Pt or Ga. This implies a synergy between Pt and Ga that results in a highly active and selective catalyst. Alkali metal dopants, such as K, are known to increase the propene selectivity and decrease coke deposition by poisoning the Brønsted acid sites present in the PDH catalysts.[9] Indeed, a slight increase is observed in propene selectivity after addition of K to the Pt and Ga containing catalysts. Finally, the bare support displays a very low activity and selectivity and is therefore regarded to be inactive. After the first PDH cycle, the conversion and selectivity of the catalysts does not drop, verifying that the catalysts are not deactivated. In fact, for the GaK, Ga, and 3Ga catalysts, the propane conversion even increases. This implies that these catalysts require an activation period, related to the exposure to oxygen at 750 °C. Indeed, by treating the catalyst with oxygen at 750 °C prior to the first propane dehydrogenation cycle, the conversion is increased from to % for the GaK catalyst. Treating the GaK catalyst at 620 °C under air prior to reaction has a lower impact and the conversion is only % for the first propane dehydrogenation cycle. Apparently, the high temperature during the regeneration is required for the Ga to remain active in the PDH the eighth cycle, the values of propane conversion and propene selectivity have dropped for all catalysts. The deactivation is the least severe for those catalysts containing both Pt and Ga. It is known that Pt-based dehydrogenation catalysts deactivate due to sintering of the metal nanoparticles, an effect provoked by the harsh conditions of the dehydrogenation reaction.[10] Therefore, it is surprising that even though the dehydrogenation and oxidation are performed at relatively high temperatures in this study, no such deactivation is observed for the PtGa catalysts the synergy between the Pt and Ga remains as these materials continue to outperform their analogues, which solely contain addition to the catalytic tests discussed in Figure 1 and Table 1, a long-term stability test consisting of approximately 150 cycles or 14 days of operation, was performed on the very active Pt3GaK catalyst. The catalytic performance of the catalyst during this experiment is shown in Figure 2. It was found that the PDH activity drops significantly during the first two days of testing, after which the catalyst performance remained stable during a twelve-day evaluation period, giving a propane conversion of % and a selectivity for propene of %, stressing the high stability of the catalyst stability experiment with the Pt3GaK catalyst, which was cycled for ca. 150 times over a 14 day period. During the first two days both the conversion and selectivity drop, after which the catalyst performance remains stable for 12 days on Raman and UV/Vis spectra have been collected during the catalytic dehydrogenation experiments and the results are summarized in Table 1. From the UV/Vis spectra Figure S4, it is concluded that the absorption increases during the first minutes on stream for the PtGaK catalyst, after which the spectra do not change anymore. In the absence of K PtGa, the darkening is a more gradual process that continues throughout the cycle. To compare the relative darkening of the different catalyst materials, an arbitrary darkening scale was designed, where 0 % darkening represented a pristine white catalyst, and 100 % darkening a completely coked catalyst, for which we used carbon nanofibers as the reference material. As Table 1 shows, the presence of K results in less darkening of the catalyst material, due to less coke being deposited. For each of the eight propane dehydrogenation cycles, a similar level of catalyst darkening is observed for all materials under Figure 3, the operando Raman spectra obtained at the end of the eighth propane dehydrogenation cycle are shown for the different investigated catalysts. Two Raman bands typical of coke are observed the so-called D disordered, at 1320 cm−1 and G band graphitic coke, at 1590 cm−1. Specific information about the nature of the coke deposits formed on the catalyst surface can be obtained from the ratio of these two Raman bands.[11] Interestingly, the presence of Pt in the catalyst material has a significant effect on the D/G ratio. In Figure 3 the lighter colored spectra represent the coke formed on Pt-containing catalysts, whereas the darker colored spectra represent the coke on their non-Pt-containing counterparts. As the Raman spectra are normalized to the G band, it is clear that the D band is more intense for the catalyst materials that do not contain Pt. When looking at the D/G ratio shown in Table 1, the catalyst materials that contain Pt and Ga have a D/G ratio of around while catalyst materials that do not have Pt in their composition have a D/G ratio of approximately A possible explanation is that Pt further dehydrogenates the carbon deposits, leading to a higher graphitic portion in the coke. However, it should be noted that the coke deposited on the support also has a D/G ratio of Similar values for the D/G ratios are obtained from the first dehydrogenation cycle, showing that the nature of the coke deposits does not Raman spectra obtained during the eighth propane dehydrogenation cycle for the different catalyst materials under investigation. The spectra are normalized with respect to the G band at 1600 cm−1. The lighter colored Raman spectra are for the Pt-containing catalysts; the darker spectra of their non-Pt-containing the eighth cycle, the catalyst materials were not regenerated, but instead collected from the reactor and analyzed by thermogravimetric analysis TGA combined with on-line mass spectrometry MS to investigate the coke deposits formed. The change of weight per temperature interval as a function of temperature is shown in Figure S5. In addition, during the combustion a distinct CO2 profile is observed for each catalyst by on-line MS analysis, which is shown in Figure S6. These profiles accurately describe the temperature where coke is combusted, which is between 300–650 °C; the weight loss corresponding with this temperature interval is included in Table 1. The amount of CO2 detected is very small for the catalyst containing only Pt, for the bare support, and for the catalysts containing K. Less coke is therefore deposited on these catalysts, in agreement with what was observed with operando UV/Vis spectroscopy. On the other hand, the absence of K and the presence of Ga results in significant amounts of coke on the catalyst surface. As Brønsted acidity is associated with the deposition of coke, the presence of GaOx may introduce acidity to the catalyst surface, resulting in catalyst coking. When K is present on the catalyst, these sites are poisoned, inhibiting the formation of coke. Note that this implies that almost no acidity is present on the bare support to start specific nature of the gallium species present on the catalyst was investigated by collecting 71Ga MAS NMR magic-angle spinning NMR and XPS X-ray photoelectron spectroscopy spectra of the fresh Pt3Ga and 3Ga catalysts Figure 4, Figure S7, and Table 2. In the NMR spectra, two peaks with chemical shifts of 151 and 15 ppm are observed relative to the signal of GaNO33, corresponding to tetrahedrally IV and octahedrally VI coordinated Ga3+, respectively.[12] The spectra show a strong resemblance to 71Ga MAS NMR spectra of a ternary oxide composed of Ga, Al, and O, as reported by Chen et al.[13] Such a mixed oxide is likely formed during the high temperatures 750 °C of the calcination step after impregnation. Chen et al. proposed that a spinel structure is formed, in which Ga3+ is preferentially located in a tetrahedral coordination. Such a tetrahedral preference of Ga3+ has been reported for several mixed oxides containing Ga and is explained by a covalent contribution to the metal oxygen bond caused by the so-called d-block contraction. As the d-orbital becomes completely filled, it ineffectively shields the nuclear charge, resulting in a higher polarization MAS NMR spectra of the fresh Pt3Ga red and 3Ga blue catalyst materials. Asterisks denote the spinning 2Chemical composition of the surface of the 3Ga and Pt3Ga catalysts as measured by XPS.[a]CatalystAl wt %O wt %Ga wt %Pt wt % measurements on the fresh samples of the Pt3Ga and 3Ga catalysts showed that only Ga3+ is present and that the concentration of Ga on the surface is only marginally higher as compared to the catalyst as a whole Table 2; wt % observed versus 3 wt %. This indicates that a significant amount of Ga is incorporated in the bulk of the support, which confirms the observation made by NMR that a mixed Al2O3–Ga2O3 oxide is formed. On the contrary, the apparent concentration of Pt is high on the surface wt % observed versus 1000 ppm, suggesting that the Pt is well dispersed on the surface. Furthermore, the presence of Pt appears to affect the distribution of Ga on the catalyst material. First of all, the concentration of Ga on the catalyst surface is higher for the Pt3Ga catalyst compared to the 3Ga catalyst wt % versus wt %. Secondly, from the 71Ga MAS NMR spectra of these two catalysts Figure 4, it is observed that a larger amount of tetrahedrally coordinated Ga3+ is present in Pt3Ga compared to the 3Ga catalyst. This suggests that the presence of Pt results in a more tetrahedral Ga3+ species on the catalyst surface. The respective XPS spectra are discussed in more detail in the Supporting Information Figure S7.Because metallic Ga is a liquid and Ga2O a volatile compound, it is important to consider the reducibility of Ga3+, especially because the dehydrogenation reaction is performed at high temperatures in a reducing atmosphere. Alternatively, a Pt–Ga alloy may be formed by hydrogen spillover from the Pt, whereby Ga3+ is reduced to Ga0, which then forms the alloy.[7,14] TPR and quasi-in situ XPS was employed to investigate the reducibility of the 3Ga and Pt3Ga catalysts. The temperature-programmed reduction TPR experiment showed that no hydrogen was being consumed while the catalyst was heated up to 700 °C under a constant hydrogen flow Figure S8. For the XPS experiment, the catalyst was reduced in a reactor, after which it was loaded into the XPS apparatus without being exposed to air. Again, no reduced Ga species were detected Figure S9. Apparently, the mixed Ga–Al oxide is too stable to be reduced at these conditions, even in the presence of chemisorption was used to study the effect of elevated temperatures on the Pt dispersion in reducing or oxidizing environments. The PtGaK catalyst was heated stepwise under either H2 or air at 350, 550, and 650 °C, without removing it from the chemisorption unit Figure S10. The Pt dispersion does not change, with an exception when the catalyst is treated at 650 °C under air; in this case the dispersion quickly collapses. During the regeneration step, the catalyst is treated at 750 °C under air, which would have similar effects on the Pt dispersion. Therefore, the Pt surface area does not correlate with the activity of the catalyst, meaning Pt is not the species mainly responsible for the PDH activity of the the trends observed with 71Ga NMR and XPS, the presence of Pt results in a higher concentration of surface tetrahedral Ga3+ species. Nevertheless, such a relatively small increase in active sites cannot account for the high activity observed for the Pt3Ga catalyst, compared to 3Ga. Since the only Pt-containing catalyst is almost inactive in the dehydrogenation reaction and the Pt dispersion drops severely after treatment under air at elevated temperatures, it is assumed that coordinately unsaturated Ga3+ species are responsible for the C=H bond activation.[15] The proposed reaction mechanisms for the dehydrogenation on Ga2O3 catalysts are discussed in a review by Copéret, in which he states that the dissociative adsorption of propane results in the formation of a surface hydroxy group and either a Ga alkyl or a Ga alkoxy species.[16] After the elimination of the β-hydrogen through the formation of hydride or a second hydroxy group, propene desorbs. However, as Pidko et al. have pointed out, the subsequent regeneration of the active sites through the formation of hydrogen is problematic, because the reduction of Ga3+ to Ga+ and H2O is energetically more favored.[17] For our catalyst material, the mixed Al–Ga oxide is too stable to be reduced, meaning that the GaH/GaOH species need to be regenerated. We postulate that the Pt assists in the recombination of the hydrogen atoms on the catalyst, making the active sites available for the following dehydrogenation the Pt3GaK catalyst was compared with a wide range of other catalyst materials reported in literature, as well as a commercial CrOx catalyst Figure S11. When comparing the propylene yield with the weight hourly space velocity, the Pt3GaK catalyst displays a superior activity, further highlighting the excellent catalytic performance of the summary, different Pt-Ga-K-containing catalyst materials have been examined for the selective dehydrogenation of propane into propene and it was found that the combination of 1000 ppm Pt and wt % Ga results in a highly active and selective catalyst. The catalyst is highly resistant to coking and remains active for prolonged reaction times. A combination of structural, morphological, and surface characterization reveals a complex catalyst material with a synergistic and bifunctional character originating from the supported Ga and Pt moieties, with Ga performing the actual dehydrogenation reaction and Pt being a unique promoting SectionThe catalyst materials under investigation have been prepared by the incipient wetness impregnation method using PtNH34NO32 %, GaNO33 %, and KNO3 >99 % as metal precursors and alumina as the support material. After impregnation, the catalyst is calcined at 750 °C under air. The catalyst materials have been characterized by a variety of techniques. Bright-field TEM analysis has been performed on a Tecnai 20 apparatus equipped with a field emission gun at 200 keV. XRD diffractograms were collected with a Bruker D2 Phaser, equipped with a Co Kα anode. For the N2-physisorption experiments a TriStar 3000 A has been used at −196 °C after drying the samples overnight. Catalytic tests have been performed on a reactor setup, which allows for combined operando UV/Vis, Raman, and on-line GC analysis.[18] A cylindrical quartz tube equipped with optical grade windows was loaded with g of catalyst material. The reaction was run at 620 °C with a flow of 9 mL min−1 of propane for 15 min, followed by a regeneration step at 750 °C with a flow of 6 % O2 in He for 30 min. During these reaction steps, operando UV/Vis and Raman spectra were collected by an Avantes 2048 UV/Vis spectrometer 50 accumulations and 70 ms exposure time and a Kaiser Optical Systems Raman spectrometer 7 accumulations and 5 s exposure time, respectively. The reaction stream was analyzed by an on-line GC, which was equipped with a flame ionization detector FID; Porabond-Q column and a thermal conductivity detector TCD; Carboxan column. Coked catalyst samples obtained after eight dehydrogenation cycles were examined on a PerkinElmer Pyris 1 TGA instrument. Between 10 and 25 mg of catalyst material was dried at 150 °C under an Ar flow and then heated under a flow of O2 from 30 to 900 °C at a ramp of 10 °C min−1. The gas stream exiting the TGA apparatus was analyzed by an Omnistar mass spectrometer from Pfeiffer Vacuum. The 71Ga MAS NMR experiments were performed in a T Bruker Avance III NMR system using an MAS rate of 16 kHz. To minimize baseline distortions, a windowless spin-echo pulse sequence was implemented, with an echo delay of 2 μs and a dead time of 5 μs.[19] The radio frequency field strength was set to 83 kHz and experiments conducted lasted for 12 days. XPS experiments were performed on a Thermo Scientific K-Alpha apparatus, equipped with an Al Kα eV X-ray anode. The catalysts were deposited on a carbon sticky tape in order to prevent charging. For analyzing the XPS spectra, the CasaXPS program is used. For the quasi-in situ experiment, the Pt3GaK catalyst was reduced for 1 h under a H2 flow at 620 °C, after which the sample was transferred to a Kratos AXIS Ultra spectrometer, equipped with a monochromatic X-ray source and a delay-line detector DLD. Spectra were obtained using the aluminum anode Al Kα= eV operating at 150 W and a background pressure of 2×10−9 bar. TPR experiments were performed on a Micromeritics Autochem II flow system, equipped with a TCD detector. g of catalyst is placed in a quartz tube, after which the sample is dried prior to being heated to 700 °C under a flow of 5 % H2 in He. A Micromeritics ASAP 2020 Accelerated Surface Area and Porosimetry System was used to analyze the Pt metal dispersion using CO adsorption. g of sample supported on a bed of quartz wool was loaded in a quartz sample tube and inserted in the instrument. The sample was pretreated prior to the chemisorption experiment by flushing nitrogen for 10 min at 35 °C, oxidizing the sample in a 10 %-oxygen-in-helium atmosphere at varying temperatures 10 °C min−1 ramp for 240 min, a reducing treatment in hydrogen at varying temperatures 10 °C min−1 for 240 min, and evacuating 5 μm Hg for 60 min at reaction temperature. The sample was analyzed with carbon monoxide at 35 °C with 15 pressure points from 25 mm Hg to 650 mm Hg. After completing the first isotherm, the sample was evacuated 10 μm Hg for one hour at 35 °C, after which a second isotherm was collected at the same conditions. The metal dispersion was calculated based on the difference of these isotherms extrapolated to 0 mm Hg, assuming a unitary ratio of carbon monoxide to surface “Shale has rocked world oil supply”, Houston Chronicle2013. 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