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Enhancing the Reaction of CO2 and H2O Using Catalysts within a Nonthermal Plasma
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-16 DOI: 10.1021/acscatal.5c00747
Piu Chawdhury, Sarayute Chansai, Matthew Conway, Joseph Parker, Matthew Lindley, Cristina E. Stere, Meenakshisundaram Sankar, Sarah J. Haigh, Ben Dennis-Smither, Sorin V. Filip, Stephen Poulston, Peter Hinde, Christopher Hawkins, Christopher Hardacre
{"title":"Enhancing the Reaction of CO2 and H2O Using Catalysts within a Nonthermal Plasma","authors":"Piu Chawdhury, Sarayute Chansai, Matthew Conway, Joseph Parker, Matthew Lindley, Cristina E. Stere, Meenakshisundaram Sankar, Sarah J. Haigh, Ben Dennis-Smither, Sorin V. Filip, Stephen Poulston, Peter Hinde, Christopher Hawkins, Christopher Hardacre","doi":"10.1021/acscatal.5c00747","DOIUrl":"https://doi.org/10.1021/acscatal.5c00747","url":null,"abstract":"The direct conversion of emitted and captured carbon dioxide into usable fuels remains a significant challenge and is a key element in the transition to net zero. Herein, we examine the reaction of CO<sub>2</sub> and H<sub>2</sub>O over Ni- and Cu-based catalysts combined with nonthermal plasma (NTP) technology. The catalysis under NTP conditions enabled significantly higher CO<sub>2</sub> conversion and product yield, which was almost six times higher than that of the plasma-only system. A maximum H<sub>2</sub> concentration of ∼2500 ppm was achieved for the Cu/ZSM5 catalyst at 17% CO<sub>2</sub> conversion. Comprehensive catalyst characterization together with the reaction performances reveals that Cu in a reduced state promotes both the CO<sub>2</sub> and H<sub>2</sub>O conversion leading to H<sub>2</sub> formation. <i>In situ</i> diffuse reflectance infrared spectroscopy (DRIFTS) coupled with mass spectrometry (MS) analysis of the gas phase products confirms that CO is the major active species to drive the water gas shift reaction to form H<sub>2</sub> in addition to the direct CO<sub>2</sub> and H<sub>2</sub>O interaction. It also explains how the different metal support interactions influence the CO adsorption and its interaction with water. Among the catalysts studied, ZSM5-supported Cu catalysts were found to be the most effective in facilitating the CO<sub>2</sub> and H<sub>2</sub>O reaction to produce H<sub>2</sub>.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"103 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837426","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Zr-Doped TiO2–x Nano-Oxide with Coordinatively Unsaturated Ti(Zr)–O Acid–Base Pairs for Efficient Propane Dehydrogenation
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-15 DOI: 10.1021/acscatal.4c07810
Zean Xie, Kemeng Song, Yu Ren, Liyu Hou, Runqi Hu, Jianmei Li, Qi Shi, Dong Li, Wencui Li, Xiaoqiang Fan, Lian Kong, Xia Xiao, Zhen Zhao
{"title":"Zr-Doped TiO2–x Nano-Oxide with Coordinatively Unsaturated Ti(Zr)–O Acid–Base Pairs for Efficient Propane Dehydrogenation","authors":"Zean Xie, Kemeng Song, Yu Ren, Liyu Hou, Runqi Hu, Jianmei Li, Qi Shi, Dong Li, Wencui Li, Xiaoqiang Fan, Lian Kong, Xia Xiao, Zhen Zhao","doi":"10.1021/acscatal.4c07810","DOIUrl":"https://doi.org/10.1021/acscatal.4c07810","url":null,"abstract":"Recently, some traditional oxide supports, such as nano TiO<sub>2</sub> and ZrO<sub>2</sub> with high surface energy, have been found to be partially reduced to generate oxygen vacancies and coordinatively unsaturated metal (M<sub>cu</sub>) cations as efficient active sites for nonoxidative propane dehydrogenation (PDH). However, the primary challenge in their industrial applications is rapid deactivation because of coke, over-reduction, and aggregation under the reaction conditions of high temperature and reducible atmosphere. Herein, we reported that cost-effective and environmentally friendly Zr-doped TiO<sub>2</sub> (Ti<sub><i>x</i></sub>Zr<sub>1</sub>) prepared by a simple coprecipitation method can be used as a highly efficient and stable catalyst for PDH. Ti<sub>3</sub>Zr<sub>1</sub> exhibited the C<sub>3</sub>H<sub>6</sub> formation rate [<i>r</i>(C<sub>3</sub>H<sub>6</sub>)] of 0.6 mmol g<sup>–1</sup> min<sup>–1</sup> at 550 °C, which was 17 times that of pure TiO<sub>2</sub>, and a deactivation constant (<i>K</i><sub>d</sub>) 2.8 times lower than that of commercial TiO<sub>2</sub>. Moderate Zr doping promotes the generation of surface active lattice oxygen, which can be reduced at a relatively low temperature to form oxygen vacancies and Ti(Zr)<sub>cu</sub>–O acid–base pairs as the active sites for PDH, and their number is in line with <i>r</i>(C<sub>3</sub>H<sub>6</sub>) of Ti<sub><i>x</i></sub>Zr<sub>1</sub> catalysts. With the increase of the Zr doping amount, the bulk crystal phase of Ti<sub><i>x</i></sub>Zr gradually transforms from Zr-doped anatase TiO<sub>2</sub> to TiZrO<sub>4</sub> via Ti<sub>2</sub>ZrO<sub>6</sub> with enhanced thermostability, which can inhibit over-reduction and aggregation of the nano-oxide.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"50 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832193","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Triangulene Synthesis Made Simple on Single-Atom-Doped Gold and Silver Surfaces 在单原子掺杂的金银表面简单合成三角木烯
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-15 DOI: 10.1021/acscatal.4c07341
Lin Chen, Johanna Rosen, Jonas Björk
{"title":"Triangulene Synthesis Made Simple on Single-Atom-Doped Gold and Silver Surfaces","authors":"Lin Chen, Johanna Rosen, Jonas Björk","doi":"10.1021/acscatal.4c07341","DOIUrl":"https://doi.org/10.1021/acscatal.4c07341","url":null,"abstract":"Triangulene, the smallest triplet-ground-state polybenzenoid, has previously been successfully synthesized by tip-manipulation experiments, employing scanning probe techniques to dehydrogenate precursor molecules under ultrahigh vacuum and low-temperature conditions. Here, we propose an alternative approach to form triangulene on (111)-facets of gold and silver doped by single noble metal atoms (Ru, Rh, Pd, or Pt), predicted by density functional theory calculations in combination with microkinetic analysis. Our results convey two key insights. First, the isolated single atoms reduce the activation energies for the dehydrogenation of dihydrotriangulene (the precursor molecule) and make the reactions more favored compared to pure Au(111) and Ag(111). In particular, we find that Rh- and Ru-doped surfaces outperform other considered single-atom-doped surfaces with nearly 100% yield of triangulene when the initial coverage of precursor is low. Second, two independent descriptors─the H and intermediate adsorption energies─are found to predict the triangulene formation activity on the single-atom-doped surfaces via scaling relations for activation and reaction energies. Based on these descriptors, a two-dimensional yield map for triangulene formation is constructed, providing valuable design insights for experimentalists. Our theoretical work suggests a straightforward thermal synthesis pathway for triangulenes, offering a more efficient alternative to prevalent tip-induced manipulation techniques and high-temperature approaches.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"121 1","pages":"6979-6988"},"PeriodicalIF":12.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832192","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Improving the Selectivity of Aldehyde–Ketone Cross-Aldol Condensation Reactions with Phosphate-Modified TiO2 Catalysts 利用磷酸盐改性 TiO2 催化剂提高醛酮交-醛醇缩合反应的选择性
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-15 DOI: 10.1021/acscatal.4c07836
Brandon Elliott Oliphant, Laura Paz Herrera, J. Will Medlin
{"title":"Improving the Selectivity of Aldehyde–Ketone Cross-Aldol Condensation Reactions with Phosphate-Modified TiO2 Catalysts","authors":"Brandon Elliott Oliphant, Laura Paz Herrera, J. Will Medlin","doi":"10.1021/acscatal.4c07836","DOIUrl":"https://doi.org/10.1021/acscatal.4c07836","url":null,"abstract":"Aldol condensation of mixtures of acetaldehyde and acetone was investigated over TiO<sub>2</sub> catalysts modified with phosphate groups of varying coverages to probe effects of surface composition on reaction selectivity. Whereas the self-aldol condensation of acetaldehyde to crotonaldehyde was observed to dominate on unmodified TiO<sub>2</sub>, we found that modifying the TiO<sub>2</sub> catalyst with surface phosphate groups resulted in improved selectivity toward cross-aldol condensation. Moreover, whereas high phosphate coverages led to lower overall condensation rates, decreasing the density of the phosphate layer resulted in activities on par with the unmodified catalyst, while maintaining higher selectivity. Characterization of reactant binding affinities and the electronic nature of the catalyst using temperature-programmed desorption, diffuse reflectance Fourier transform spectroscopy, and X-ray photoelectron spectroscopy suggested that the changes in selectivity stem from changes in reactant binding driven by the phosphates modifying the electronic nature of the catalyst. This approach represents a promising path toward tuning selectivity for aldol condensation reactions in heterogeneous systems with a relatively facile catalyst modification technique.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"32 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832194","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Correction to “Deoxygenation of 1° and 2° Amides with Ce[N(SiMe3)2]3(THF)3 under Mild Conditions”
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-15 DOI: 10.1021/acscatal.5c02346
Md Jabed Hossain, Brij Kumar Shah, Shabana Khan
{"title":"Correction to “Deoxygenation of 1° and 2° Amides with Ce[N(SiMe3)2]3(THF)3 under Mild Conditions”","authors":"Md Jabed Hossain, Brij Kumar Shah, Shabana Khan","doi":"10.1021/acscatal.5c02346","DOIUrl":"https://doi.org/10.1021/acscatal.5c02346","url":null,"abstract":"The Ce[N(SiMe&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]&lt;sub&gt;3&lt;/sub&gt;(THF)&lt;sub&gt;3&lt;/sub&gt; should be read as Ce[N(SiMe&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]&lt;sub&gt;3&lt;/sub&gt; in this work. There is no THF coordinated with the cerium center as per the analytical data and the molecular structure provided in the corrected Supporting Information. The stoichiometric reactions (Scheme 9) are also repeated, and revised spectra are provided in the corrected Supporting Information. All the catalytic reactions are repeated with the Ce[N(SiMe&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]&lt;sub&gt;3&lt;/sub&gt; as per the mol % calculation mentioned in the previous submission, and there is no significant change in the yields. The following text should be added on page 13583 under the subheading of EXPERIMENTAL MECHANISTIC ASPECTS: “The &lt;sup&gt;1&lt;/sup&gt;H NMR spectrum of this mixture was inconclusive, but a small peak at 581.6802 was observed in the mass spectrum of a 1:1 mixture of Ce[N(SiMe&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]&lt;sub&gt;3&lt;/sub&gt; with benzamide, which corresponds to the cerium mono-amidate complex.” The following text should be added on page 13583 under the subheading of EXPERIMENTAL MECHANISTIC ASPECTS: “The mass spectrometric data showed an intense peak at &lt;i&gt;m&lt;/i&gt;/&lt;i&gt;z&lt;/i&gt; 501.1758, which matches well with the mass of the cerium tris-amidate complex of benzamide (Figure S51).” The following text should be added in the footnote of Scheme 6: &lt;sup&gt;a&lt;/sup&gt;Yields were determined by integrating &lt;sup&gt;1&lt;/sup&gt;H NMR spectra in the presence of an internal standard (mesitylene). &lt;sup&gt;b&lt;/sup&gt;Reaction time of 24 h. &lt;sup&gt;c&lt;/sup&gt;Catalyst (1 mol %) and 4 h reaction time. &lt;sup&gt;d&lt;/sup&gt;&lt;b&gt;2b&lt;/b&gt;, &lt;b&gt;2d&lt;/b&gt; , and &lt;b&gt;2g&lt;/b&gt; require high temperature (∼100 °C) and 24 h reaction time. The following text should be added in the footnote of Scheme 7: &lt;sup&gt;a&lt;/sup&gt;Yields were determined by integrating &lt;sup&gt;1&lt;/sup&gt;H NMR spectra in the presence of an internal standard (mesitylene). &lt;sup&gt;b&lt;/sup&gt;&lt;b&gt;2j&lt;/b&gt; and &lt;b&gt;2n&lt;/b&gt; require high temperature (∼100 °C) and 24 h reaction time. The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acscatal.5c02346. Experimental procedures and characterization data, kinetic studies, NMR spectra (&lt;sup&gt;1&lt;/sup&gt;H NMR, &lt;sup&gt;13&lt;/sup&gt;C NMR, &lt;sup&gt;29&lt;/sup&gt;Si NMR, and &lt;sup&gt;11&lt;/sup&gt;B NMR), mass spectra, and Raman spectra (PDF) Correction to “Deoxygenation\u0000of 1° and\u00002° Amides with Ce[N(SiMe&lt;sub&gt;3&lt;/sub&gt;)&lt;sub&gt;2&lt;/sub&gt;]&lt;sub&gt;3&lt;/sub&gt;(THF)&lt;sub&gt;3&lt;/sub&gt; under Mild Conditions” &lt;span&gt; 4 &lt;/span&gt;&lt;span&gt; views &lt;/span&gt; &lt;span&gt; 0 &lt;/span&gt;&lt;span&gt; shares &lt;/span&gt; &lt;span&gt; 0 &lt;/span&gt;&lt;span&gt; downloads &lt;/span&gt; Most electronic Supporting Information files are available without a subscription to ACS Web Editions. Such files may be downloaded by article for research use (if there is a public use license linked to the relevant article, that license may permit other uses). Permission may be obtained from ACS for other uses through requests via the RightsLink permission system: http://pubs.acs.org/page/copyright/permissions.html. This article ","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"50 1","pages":"6989-6989"},"PeriodicalIF":12.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832196","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Insights into the Mechanism of High CO2 Selectivity over Co2C-Based Fischer–Tropsch to Olefins
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-15 DOI: 10.1021/acscatal.4c06992
Da Wang, Guangbo Liu, Chuanhui Zhang, Chao Feng, Jinhu Wu, Song Chen, Wenjie Xiang, Hao Huang, Zhihao Liu, Noritatsu Tsubaki
{"title":"Insights into the Mechanism of High CO2 Selectivity over Co2C-Based Fischer–Tropsch to Olefins","authors":"Da Wang, Guangbo Liu, Chuanhui Zhang, Chao Feng, Jinhu Wu, Song Chen, Wenjie Xiang, Hao Huang, Zhihao Liu, Noritatsu Tsubaki","doi":"10.1021/acscatal.4c06992","DOIUrl":"https://doi.org/10.1021/acscatal.4c06992","url":null,"abstract":"The reasons for the too high CO<sub>2</sub> selectivity (near 50 C %) in Co<sub>2</sub>C-based Fischer–Tropsch to olefins (FTO) are not clear. Water–gas-shift (WGS) side reaction is thought to be responsible for this, but in-depth research is lacking. Here, we revealed the mechanism of the too high CO<sub>2</sub> selectivity in Co<sub>2</sub>C-based FTO. Kinetic studies showed that WGS reaction was more likely to occur than the hydrocarbon production reaction. In addition, a too severe WGS reaction would result in the formation of an H<sub>2</sub>-enriched and CO-deficient environment on the catalyst surface, which was not favorable for the generation of light olefins. Catalyst characterization results proved that the severe WGS reaction could also lead to the transformation of prismatic Co<sub>2</sub>C to spherical Co<sub>2</sub>C. Theoretical calculations demonstrated that prismatic Co<sub>2</sub>C (020) and Co<sub>2</sub>C (101) facets were dominant crystal facets for both FTO and WGS reactions. Furthermore, in situ diffuse reflectance infrared Fourier transform spectroscopy experiments found that the H<sub>2</sub>O produced in FTO completely participated in the WGS reaction. This clearly revealed why the CO<sub>2</sub> selectivity was close to 50 C % in FTO. Therefore, we believed that accelerating the desorption of H<sub>2</sub>O on the catalyst surface and preventing its readsorption are the key elements for inhibiting CO<sub>2</sub> formation in FTO.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"407 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837429","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Advanced Deposition Methods for Mixed Metal Alloys and Hydroxides as High-Performance Catalysts for the Hydrogen Evolution Reaction
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-15 DOI: 10.1021/acscatal.5c00291
Ariel Friedman, Kevin Yang, Huanyao Ge, Sanjeev Mukerjee
{"title":"Advanced Deposition Methods for Mixed Metal Alloys and Hydroxides as High-Performance Catalysts for the Hydrogen Evolution Reaction","authors":"Ariel Friedman, Kevin Yang, Huanyao Ge, Sanjeev Mukerjee","doi":"10.1021/acscatal.5c00291","DOIUrl":"https://doi.org/10.1021/acscatal.5c00291","url":null,"abstract":"Alkaline water and anion-exchange membrane electrolyzers are considered leading solutions for the large-scale production of hydrogen due to their lower capital costs. In recent years, numerous hydrogen evolution electrocatalysts have been developed, primarily by alloying nickel with other transition metals. Despite these advancements, stability remains a challenge due to the low intrinsic corrosion resistance of these alloys. In this work, we present an advanced synthesis method that incorporates an amorphous copper hydroxide phase within a nickel–copper alloy using a pH-trap mechanism. This approach prevents the formation of long-range ordered and dense catalysts, resulting in a significantly higher surface area and enhanced catalytic activity. A detailed mechanism was proposed to explain this deposition process. The use of copper eliminates corrosion risks due to its thermodynamic stability in alkaline conditions, even at relatively high potentials. Accelerated stress tests demonstrate that the NiCu catalyst is stable under both continuous and intermittent conditions, in both inert and oxygen atmospheres, positioning it as one of the most active and stable HER catalysts in alkaline media. Furthermore, the pH-trap deposition (pTD) method developed here can be applied to a variety of materials to tailor their physical and chemical properties.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"4 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837431","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Unprecedented Dual Radical Initiation in Visible-Light Photoredox-Catalyzed X–H (X = Si and B) Insertions of Sulfoxonium Ylides
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-15 DOI: 10.1021/acscatal.5c01823
Mengyu Xu, Yujing Wang, Rui Fu, Xiaoguang Bao
{"title":"Unprecedented Dual Radical Initiation in Visible-Light Photoredox-Catalyzed X–H (X = Si and B) Insertions of Sulfoxonium Ylides","authors":"Mengyu Xu, Yujing Wang, Rui Fu, Xiaoguang Bao","doi":"10.1021/acscatal.5c01823","DOIUrl":"https://doi.org/10.1021/acscatal.5c01823","url":null,"abstract":"Unusual chameleonic roles of sulfoxonium ylides, acting as both radical initiators and radical acceptors, are revealed via synergistic experimental and computational studies for the visible-light photoredox-catalyzed Si–H insertion of sulfoxonium ylides with hydrosilanes. Remarkably, when sulfoxonium ylides play the role of radical initiator, an unprecedented dual radical initiation is proposed, in which two radical species, generated in a photoredox catalytic loop via single-electron oxidation and single-electron reduction, respectively, can both trigger H atom transfer processes with hydrosilanes to afford a silyl radical. Subsequently, the yielded silyl radical can attack the C═S moiety of sulfoxonium ylide to fulfill a radical chain mechanistic pathway to furnish the desired product, where sulfoxonium ylides perform as a radical acceptor. This protocol employs easily accessible reagents and demonstrates a wide substrate scope with satisfied yields under benign conditions. Additionally, the construction of C–B bonds via analogous visible-light photoredox-catalyzed B–H insertion of sulfoxonium ylides with amine boranes is also realized.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Defect-rich Birnessite Ultrathin Nanosheet Array Armed with Fe-Phytate Complex Enables Boosted and Long-Lasting Seawater Oxidation at Industrial-Level Current Density 富含缺陷的桦褐铁矿超薄纳米片阵列与铁-hytate复合物可在工业级电流密度下实现高效持久的海水氧化作用
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-15 DOI: 10.1021/acscatal.5c00581
Yuting Yang, Jixin Li, Wei Qiao, Han Yang, Yuqi Huang, Fengli Li, Yu Yu, Jingyun Fang, Ping Li
{"title":"Defect-rich Birnessite Ultrathin Nanosheet Array Armed with Fe-Phytate Complex Enables Boosted and Long-Lasting Seawater Oxidation at Industrial-Level Current Density","authors":"Yuting Yang, Jixin Li, Wei Qiao, Han Yang, Yuqi Huang, Fengli Li, Yu Yu, Jingyun Fang, Ping Li","doi":"10.1021/acscatal.5c00581","DOIUrl":"https://doi.org/10.1021/acscatal.5c00581","url":null,"abstract":"Seawater electrolysis is appealing for mass production of high-purity H<sub>2</sub>, yet it remains challenging in engineering an efficient and robust oxygen evolution reaction (OER) anode to avoid undesired chloride oxidation reactions and resist chloride corrosion. Herein, we report a multilayered electrode with a Fe-phytate (Fe-PA) complex armor capped on the defect-rich Ni-doped δ-MnO<sub>2</sub> ultrathin nanosheet array aligned on 3D macroporous Ni foam for boosted and sustained seawater oxidation at an industrial-level current density. From comprehensive experimental and theoretical investigations, the integration of the defect-rich Ni-MnO<sub>2</sub> ultrathin nanosheet array configuration with a surface Fe-PA modification can provide abundant catalytic sites featuring an optimized electronic structure to promote the rate-determining step of *OH deprotonation to inherently boost the OER, and meanwhile impart superhydrophilicity and quasi-superaerophobicity to accelerate electrolyte infiltration and bubble detachment for facilitated mass transport. Impressively, the multilayered architecture comprising an inherently anticorrosive δ-MnO<sub>2</sub> core and Fe-PA complex armor could cooperatively contribute to promoting corrosion resistance via effective chloride repelling. This work opens up a promising avenue for constructing MnO<sub>2</sub>-based materials toward promoted and long-lasting seawater oxidation via geometric and electronic modulation, which represents a significant step in advancing seawater electrolysis technology.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"3 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143832195","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
In Situ Selective Site-Blocking Dictates Benzene Partial Hydrogenation to Cyclohexene on Zn-Promoted Ru-Based Catalysts
IF 12.9 1区 化学
ACS Catalysis Pub Date : 2025-04-15 DOI: 10.1021/acscatal.5c00950
Zheng-Yang Hu, Zi-Zhan He, Lin Chen, Cheng Shang, Zhi-Pan Liu
{"title":"In Situ Selective Site-Blocking Dictates Benzene Partial Hydrogenation to Cyclohexene on Zn-Promoted Ru-Based Catalysts","authors":"Zheng-Yang Hu, Zi-Zhan He, Lin Chen, Cheng Shang, Zhi-Pan Liu","doi":"10.1021/acscatal.5c00950","DOIUrl":"https://doi.org/10.1021/acscatal.5c00950","url":null,"abstract":"The partial hydrogenation of benzene to cyclohexene (CHE) represents a long-standing challenge in catalysis. Although Zn-promoted Ru-based catalysts were patented decades ago for achieving a top record of 50% CHE yield, the active sites and mechanistic origins of selectivity, specifically why the unsaturated C–C bonds in benzene are targeted over those in CHE, have remained unresolved despite four decades of research. Here, we employ large-scale machine-learning-driven global optimization to explore millions of Ru and Ru–Zn structure candidates and a complete benzene hydrogenation reaction network under realistic reaction conditions, that is, 50 atm H<sub>2</sub> pressures, aqueous Zn<sup>2+</sup> solution. We reveal that (i) Zn<sup>2+</sup> ions selectively deposit on corrugated Ru surfaces, for example, Ru(101̅0) and (101̅1), where they inhibit deep hydrogenation by blocking too active sites; (ii) partial hydrogenation occurs exclusively on close-packed Ru(0001) terraces covered with one monolayer of chemisorbed H atoms. Microkinetics simulation further confirms that the presence of Zn enhances the CHE yield from 0% to 50% by poisoning corrugated surfaces in Ru nanoparticles. Building on these atomistic insights, we propose that introducing tensile strain 2% into the Ru lattice can elevate the CHE yield to 60% with 100% CHE selectivity, highlighting the potential for tailored catalyst supports to maximize performance.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"302 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-04-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143837430","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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