Quantifying how the cis/trans ratio of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide impacts the growth kinetics, composition and local structure of SSZ-39†

IF 3.9 3区 化学 Q2 CHEMISTRY, MULTIDISCIPLINARY RSC Advances Pub Date : 2025-03-14 DOI:10.1039/D4RA08620A
Zheng Cui, Charles E. Umhey, Onyinyechukwu C. Ukagha, Motunrayo Ogunleye, Jean-Sabin McEwen and Daniel F. Shantz
{"title":"Quantifying how the cis/trans ratio of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide impacts the growth kinetics, composition and local structure of SSZ-39†","authors":"Zheng Cui, Charles E. Umhey, Onyinyechukwu C. Ukagha, Motunrayo Ogunleye, Jean-Sabin McEwen and Daniel F. Shantz","doi":"10.1039/D4RA08620A","DOIUrl":null,"url":null,"abstract":"<p >This work integrates experiments and computational methods to quantify how the <em>cis</em>/<em>trans</em> ratio of the OSDA used in SSZ-39 synthesis impacts the crystallization kinetics, material properties, and final product composition. The crystallization kinetics increase by 30% when increasing the <em>trans</em> isomer content from 14% to 80%. Per prior work, in all cases based on the synthesis gel composition and product yield aluminum is the limiting reagent, and the absence of any amorphous material detected in the time resolved PXRD studies leads us to conclude that FAU dissolution is the rate limiting step in the formation of SSZ-39 in this synthesis protocol. The TGA and NMR results suggest that the <em>trans</em> isomer of OSDA is selectively incorporated into the product. The NMR binding studies, and corresponding DFT-based results show that the <em>trans</em> isomer binds to FAU more strongly than the <em>cis</em> isomer, providing one possible explanation for this enhancement in kinetics and preferential uptake of the <em>trans</em> isomer. The EDS analysis indicates that the Si/Al ratios are between 7.7 and 8.6 at low and high <em>trans</em> OSDA content, indicating zeolite composition is mildly sensitive to the <em>trans</em> isomer content. EDS results show this decrease in aluminum content leads to a corresponding decrease in sodium uptake. DFT-based calculations confirm OSDA–sodium interactions cannot explain any decrease in sodium uptake, reinforcing lower aluminum content as the cause of lower sodium uptake. Preliminary cobalt titration experiments show a surprisingly low cobalt uptake but also show a clear dependence of the cobalt uptake on the solution pH.</p>","PeriodicalId":102,"journal":{"name":"RSC Advances","volume":" 10","pages":" 7962-7972"},"PeriodicalIF":3.9000,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/ra/d4ra08620a?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"RSC Advances","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/ra/d4ra08620a","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

This work integrates experiments and computational methods to quantify how the cis/trans ratio of the OSDA used in SSZ-39 synthesis impacts the crystallization kinetics, material properties, and final product composition. The crystallization kinetics increase by 30% when increasing the trans isomer content from 14% to 80%. Per prior work, in all cases based on the synthesis gel composition and product yield aluminum is the limiting reagent, and the absence of any amorphous material detected in the time resolved PXRD studies leads us to conclude that FAU dissolution is the rate limiting step in the formation of SSZ-39 in this synthesis protocol. The TGA and NMR results suggest that the trans isomer of OSDA is selectively incorporated into the product. The NMR binding studies, and corresponding DFT-based results show that the trans isomer binds to FAU more strongly than the cis isomer, providing one possible explanation for this enhancement in kinetics and preferential uptake of the trans isomer. The EDS analysis indicates that the Si/Al ratios are between 7.7 and 8.6 at low and high trans OSDA content, indicating zeolite composition is mildly sensitive to the trans isomer content. EDS results show this decrease in aluminum content leads to a corresponding decrease in sodium uptake. DFT-based calculations confirm OSDA–sodium interactions cannot explain any decrease in sodium uptake, reinforcing lower aluminum content as the cause of lower sodium uptake. Preliminary cobalt titration experiments show a surprisingly low cobalt uptake but also show a clear dependence of the cobalt uptake on the solution pH.

Abstract Image

查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
求助全文
约1分钟内获得全文 去求助
来源期刊
RSC Advances
RSC Advances chemical sciences-
CiteScore
7.50
自引率
2.60%
发文量
3116
审稿时长
1.6 months
期刊介绍: An international, peer-reviewed journal covering all of the chemical sciences, including multidisciplinary and emerging areas. RSC Advances is a gold open access journal allowing researchers free access to research articles, and offering an affordable open access publishing option for authors around the world.
期刊最新文献
Low-dielectric benzocyclobutenyl polysiloxane resin: spatial structure design and photosensitive patterning performance† Highly sensitive evanescent wave SERS probe based on exposed-core optical fibers and its application† Optimizing the white light emission in the solid state isatin and thiazole based molecular hybrids by introduction of variety of substituents on isatin and thiazole ring systems† Quantifying how the cis/trans ratio of N,N-dimethyl-3,5-dimethylpiperidinium hydroxide impacts the growth kinetics, composition and local structure of SSZ-39† Non-enzymatic dopamine detection using iron doped ZIF-8-based electrochemical sensor
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1