ACS Catalysis 最新文献_第7页

Crystal Phase-Dependent Dispersion and Catalysis of the Ag Species Supported on TiO2 for CO Oxidation with Excess Oxygen

IF 11.3 1区化学

ACS Catalysis Pub Date : 2025-01-29 DOI: 10.1021/acscatal.4c0738110.1021/acscatal.4c07381

Cen Tang, Qiuyu Huang, Ziwei Wang, Yongfang Sun*, Jieqiong Ding, Fei Wang, Weixin Huang, Xiaodong Wen* and Zhenhua Zhang*,

{"title":"Crystal Phase-Dependent Dispersion and Catalysis of the Ag Species Supported on TiO2 for CO Oxidation with Excess Oxygen","authors":"Cen Tang, Qiuyu Huang, Ziwei Wang, Yongfang Sun*, Jieqiong Ding, Fei Wang, Weixin Huang, Xiaodong Wen* and Zhenhua Zhang*, ","doi":"10.1021/acscatal.4c0738110.1021/acscatal.4c07381","DOIUrl":"https://doi.org/10.1021/acscatal.4c07381https://doi.org/10.1021/acscatal.4c07381","url":null,"abstract":"Oxidation-induced dispersion of supported metal catalysts has been frequently observed in gas–solid heterogeneous reactions, while precise tailoring of the structures of restructured metals remains challenging. Here, we successfully demonstrated the feasibility of using different TiO2 crystal phases to tune the nanostructures of restructured silver species upon CO oxidation with excess O2. Compared to pure anatase and rutile phases, a mixture of anatase and rutile phases (m-TiO2) is more advantageous for the dispersion of supported Ag species, with a particle size distribution of 3.5 ± 0.2 nm, which is closely related to the surface OH group and defect concentrations of TiO2 supports. Spectroscopic characterizations clearly reveal the CO oxidation catalyzed by the Ag/TiO2 catalysts following a Mars–van Krevelen mechanism. Consequently, in addition to the Ag dispersion, a Ag/m-TiO2 catalyst with higher active oxygen species contents and correspondingly better reducibility, relevant for CO activation and reactivity, contributes to better catalytic performance in CO oxidation. These results highlight the potential of crystal phases of oxide supports in tailoring oxidation-induced restructuring to develop efficient heterogeneous catalysts for applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 3","pages":"2630–2641 2630–2641"},"PeriodicalIF":11.3,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143259054","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

Ni/Cu Cocatalyzed Asymmetric Hydrogenation of Amino Ketones with Water as a Hydrogen Source

IF 11.3 1区化学

ACS Catalysis Pub Date : 2025-01-29 DOI: 10.1021/acscatal.4c0617910.1021/acscatal.4c06179

Qiongtong Yang, Yao Deng, Hekun Yang, Hongyan Zhao, Pengjie Yao, Jingchao Chen*, Zhifeng Ma* and Baomin Fan*,

{"title":"Ni/Cu Cocatalyzed Asymmetric Hydrogenation of Amino Ketones with Water as a Hydrogen Source","authors":"Qiongtong Yang, Yao Deng, Hekun Yang, Hongyan Zhao, Pengjie Yao, Jingchao Chen*, Zhifeng Ma* and Baomin Fan*, ","doi":"10.1021/acscatal.4c0617910.1021/acscatal.4c06179","DOIUrl":"https://doi.org/10.1021/acscatal.4c06179https://doi.org/10.1021/acscatal.4c06179","url":null,"abstract":"While the asymmetric hydrogenation of protected amino ketones provides straightforward access to chiral amino alcohols, a significant gap exists in developing asymmetric transfer hydrogenation with cost-effective, nonprecious metal catalysts that ensure safety and sustainability. Herein, we present a Ni/Cu cocatalyzed asymmetric reduction of amino ketones employing water as the hydrogen source. This cocatalytic system efficiently converts a broad range of α- and β-amino ketones into their corresponding chiral amino alcohols with high yields and enantioselectivities. The method’s scalability was demonstrated by a successful gram-scale reaction alongside versatile derivatizations leading to eight pharmaceuticals, underscoring the method’s synthetic utility. This approach offers a safe, cost-effective, and easy-handling route to enantioenriched chiral amino alcohols, providing a valuable platform for synthesizing chiral pharmaceuticals and ligands. Additionally, mechanistic insights provided by an in-depth DFT study revealed that the high enantioselectivity and catalytic activity are primarily driven by steric effects within the Ni/Cu catalytic system.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 3","pages":"2666–2676 2666–2676"},"PeriodicalIF":11.3,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258983","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

A Model Approach to Uncover the Role of the IrOx Crystallographic Structure and Chemistry on OER Activity and Stability via Annealing a Sacrificial Template

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-29 DOI: 10.1021/acscatal.4c06396

Delphine Clauss, Vincent Martin, Jaysen Nelayah, Raphaël Chattot, Pierre Bordet, Jakub Drnec, Marta Mirolo, Laetitia Dubau, Frédéric Maillard

{"title":"A Model Approach to Uncover the Role of the IrOx Crystallographic Structure and Chemistry on OER Activity and Stability via Annealing a Sacrificial Template","authors":"Delphine Clauss, Vincent Martin, Jaysen Nelayah, Raphaël Chattot, Pierre Bordet, Jakub Drnec, Marta Mirolo, Laetitia Dubau, Frédéric Maillard","doi":"10.1021/acscatal.4c06396","DOIUrl":"https://doi.org/10.1021/acscatal.4c06396","url":null,"abstract":"Iridium oxide nanoparticles (IrOx NPs) hold promise to lower the catalyst cost of proton-exchange membrane water electrolyzers (PEMWE). However, their enhanced oxygen evolution reaction (OER) activity often comes at the expense of stability. Achieving a delicate balance between these two conflicting properties requires a comprehensive understanding of how the structural, morphological, and chemical characteristics of IrOx NPs influence them. To address this challenge, we synthesized IrOx NPs supported on carbon (IrOx/C), and annealed them in air at temperatures ranging from 340 to 870 °C. We obtained a library of materials, ranging from small, amorphous IrOx NPs supported on carbon to larger self-supported crystalline IrO2. Using this library, we evidence the critical role of the IrOx particle size, crystallinity and chemistry on both the OER activity and catalyst stability. We further identify that an annealing temperature of 520 °C provides an optimal balance between OER activity and stability, and we demonstrate size control of unsupported small IrO2 NPs at temperatures above 500 °C, highlighting the significant role of the sacrificial support in shaping nanostructured IrO2 catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"39 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057200","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

Switching Methane Selectivity in Carbon Dioxide Electroreduction via Confining Copper(I) Oxide Nanocubes by Polyimine Shells

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-29 DOI: 10.1021/acscatal.4c07082

Jong-Yeong Jung, Junsoo Lee, Yohan Kim, Dongwoo Shin, Jonghyeok Park, Sungjoo Kim, Hye Ryung Byon, Hyungjun Kim, Hyunjoon Song

{"title":"Switching Methane Selectivity in Carbon Dioxide Electroreduction via Confining Copper(I) Oxide Nanocubes by Polyimine Shells","authors":"Jong-Yeong Jung, Junsoo Lee, Yohan Kim, Dongwoo Shin, Jonghyeok Park, Sungjoo Kim, Hye Ryung Byon, Hyungjun Kim, Hyunjoon Song","doi":"10.1021/acscatal.4c07082","DOIUrl":"https://doi.org/10.1021/acscatal.4c07082","url":null,"abstract":"The selective formation of C1 or C2 products remains a significant challenge in electrochemical carbon dioxide reduction reaction (eCO2RR). Attaining large-scale CH4 production is significant in advancing a carbon-neutral economy. However, hydrogenation simultaneously competes with C–C coupling and hydrogen evolution reactions, which poses substantial obstacles in steering a single reaction pathway. Herein, we promote CH4 production by encapsulating Cu2O nanocubes with polyimine shells serving as diffusion barriers. The simple encapsulation with 50 nm thick shells significantly enhances the CH4-to-C2H4 ratio of Cu2O nanocatalysts from 0.14 to 8.9, achieving a Faradaic efficiency of 50.2% for CH4 at a partial current density of −201 mA cm–2 in alkaline electrolytes. In situ X-ray absorption and Raman spectroscopy demonstrate that encapsulation promotes the accumulation of surface-adsorbed hydroxide ions and significantly stabilized Cu(I) species throughout eCO2RR, with over 82% Cu(I) retention at −200 mA cm–2 for 2 h. Density functional theory calculations support the high coverage of surface-adsorbed hydroxide ions favored *CO hydrogenation over dimerization. This shell encapsulation strategy provides a straightforward approach to modulating eCO2RR mechanisms and product selectivity by tuning local chemical environments and Cu-oxidation states.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"72 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057201","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

Ni/Cu Cocatalyzed Asymmetric Hydrogenation of Amino Ketones with Water as a Hydrogen Source

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-29 DOI: 10.1021/acscatal.4c06179

Qiongtong Yang, Yao Deng, Hekun Yang, Hongyan Zhao, Pengjie Yao, Jingchao Chen, Zhifeng Ma, Baomin Fan

{"title":"Ni/Cu Cocatalyzed Asymmetric Hydrogenation of Amino Ketones with Water as a Hydrogen Source","authors":"Qiongtong Yang, Yao Deng, Hekun Yang, Hongyan Zhao, Pengjie Yao, Jingchao Chen, Zhifeng Ma, Baomin Fan","doi":"10.1021/acscatal.4c06179","DOIUrl":"https://doi.org/10.1021/acscatal.4c06179","url":null,"abstract":"While the asymmetric hydrogenation of protected amino ketones provides straightforward access to chiral amino alcohols, a significant gap exists in developing asymmetric transfer hydrogenation with cost-effective, nonprecious metal catalysts that ensure safety and sustainability. Herein, we present a Ni/Cu cocatalyzed asymmetric reduction of amino ketones employing water as the hydrogen source. This cocatalytic system efficiently converts a broad range of α- and β-amino ketones into their corresponding chiral amino alcohols with high yields and enantioselectivities. The method’s scalability was demonstrated by a successful gram-scale reaction alongside versatile derivatizations leading to eight pharmaceuticals, underscoring the method’s synthetic utility. This approach offers a safe, cost-effective, and easy-handling route to enantioenriched chiral amino alcohols, providing a valuable platform for synthesizing chiral pharmaceuticals and ligands. Additionally, mechanistic insights provided by an in-depth DFT study revealed that the high enantioselectivity and catalytic activity are primarily driven by steric effects within the Ni/Cu catalytic system.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"36 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143057198","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

Crystal Phase-Dependent Dispersion and Catalysis of the Ag Species Supported on TiO2 for CO Oxidation with Excess Oxygen 在过量氧气的 CO 氧化过程中，TiO2 上支持的 Ag 物种的晶相依赖性分散和催化作用

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-29 DOI: 10.1021/acscatal.4c07381

Cen Tang, Qiuyu Huang, Ziwei Wang, Yongfang Sun, Jieqiong Ding, Fei Wang, Weixin Huang, Xiaodong Wen, Zhenhua Zhang

{"title":"Crystal Phase-Dependent Dispersion and Catalysis of the Ag Species Supported on TiO2 for CO Oxidation with Excess Oxygen","authors":"Cen Tang, Qiuyu Huang, Ziwei Wang, Yongfang Sun, Jieqiong Ding, Fei Wang, Weixin Huang, Xiaodong Wen, Zhenhua Zhang","doi":"10.1021/acscatal.4c07381","DOIUrl":"https://doi.org/10.1021/acscatal.4c07381","url":null,"abstract":"Oxidation-induced dispersion of supported metal catalysts has been frequently observed in gas–solid heterogeneous reactions, while precise tailoring of the structures of restructured metals remains challenging. Here, we successfully demonstrated the feasibility of using different TiO2 crystal phases to tune the nanostructures of restructured silver species upon CO oxidation with excess O2. Compared to pure anatase and rutile phases, a mixture of anatase and rutile phases (m-TiO2) is more advantageous for the dispersion of supported Ag species, with a particle size distribution of 3.5 ± 0.2 nm, which is closely related to the surface OH group and defect concentrations of TiO2 supports. Spectroscopic characterizations clearly reveal the CO oxidation catalyzed by the Ag/TiO2 catalysts following a Mars–van Krevelen mechanism. Consequently, in addition to the Ag dispersion, a Ag/m-TiO2 catalyst with higher active oxygen species contents and correspondingly better reducibility, relevant for CO activation and reactivity, contributes to better catalytic performance in CO oxidation. These results highlight the potential of crystal phases of oxide supports in tailoring oxidation-induced restructuring to develop efficient heterogeneous catalysts for applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"62 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055465","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

A Model Approach to Uncover the Role of the IrOx Crystallographic Structure and Chemistry on OER Activity and Stability via Annealing a Sacrificial Template

IF 11.3 1区化学

ACS Catalysis Pub Date : 2025-01-29 DOI: 10.1021/acscatal.4c0639610.1021/acscatal.4c06396

Delphine Clauss*, Vincent Martin, Jaysen Nelayah, Raphaël Chattot, Pierre Bordet, Jakub Drnec, Marta Mirolo, Laetitia Dubau and Frédéric Maillard*,

{"title":"A Model Approach to Uncover the Role of the IrOx Crystallographic Structure and Chemistry on OER Activity and Stability via Annealing a Sacrificial Template","authors":"Delphine Clauss*, Vincent Martin, Jaysen Nelayah, Raphaël Chattot, Pierre Bordet, Jakub Drnec, Marta Mirolo, Laetitia Dubau and Frédéric Maillard*, ","doi":"10.1021/acscatal.4c0639610.1021/acscatal.4c06396","DOIUrl":"https://doi.org/10.1021/acscatal.4c06396https://doi.org/10.1021/acscatal.4c06396","url":null,"abstract":"Iridium oxide nanoparticles (IrOx NPs) hold promise to lower the catalyst cost of proton-exchange membrane water electrolyzers (PEMWE). However, their enhanced oxygen evolution reaction (OER) activity often comes at the expense of stability. Achieving a delicate balance between these two conflicting properties requires a comprehensive understanding of how the structural, morphological, and chemical characteristics of IrOx NPs influence them. To address this challenge, we synthesized IrOx NPs supported on carbon (IrOx/C), and annealed them in air at temperatures ranging from 340 to 870 °C. We obtained a library of materials, ranging from small, amorphous IrOx NPs supported on carbon to larger self-supported crystalline IrO2. Using this library, we evidence the critical role of the IrOx particle size, crystallinity and chemistry on both the OER activity and catalyst stability. We further identify that an annealing temperature of 520 °C provides an optimal balance between OER activity and stability, and we demonstrate size control of unsupported small IrO2 NPs at temperatures above 500 °C, highlighting the significant role of the sacrificial support in shaping nanostructured IrO2 catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 3","pages":"2654–2665 2654–2665"},"PeriodicalIF":11.3,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258985","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

Switching Methane Selectivity in Carbon Dioxide Electroreduction via Confining Copper(I) Oxide Nanocubes by Polyimine Shells

IF 11.3 1区化学

ACS Catalysis Pub Date : 2025-01-29 DOI: 10.1021/acscatal.4c0708210.1021/acscatal.4c07082

Jong-Yeong Jung, Junsoo Lee, Yohan Kim, Dongwoo Shin, Jonghyeok Park, Sungjoo Kim, Hye Ryung Byon*, Hyungjun Kim* and Hyunjoon Song*,

{"title":"Switching Methane Selectivity in Carbon Dioxide Electroreduction via Confining Copper(I) Oxide Nanocubes by Polyimine Shells","authors":"Jong-Yeong Jung, Junsoo Lee, Yohan Kim, Dongwoo Shin, Jonghyeok Park, Sungjoo Kim, Hye Ryung Byon*, Hyungjun Kim* and Hyunjoon Song*, ","doi":"10.1021/acscatal.4c0708210.1021/acscatal.4c07082","DOIUrl":"https://doi.org/10.1021/acscatal.4c07082https://doi.org/10.1021/acscatal.4c07082","url":null,"abstract":"The selective formation of C1 or C2 products remains a significant challenge in electrochemical carbon dioxide reduction reaction (eCO2RR). Attaining large-scale CH4 production is significant in advancing a carbon-neutral economy. However, hydrogenation simultaneously competes with C–C coupling and hydrogen evolution reactions, which poses substantial obstacles in steering a single reaction pathway. Herein, we promote CH4 production by encapsulating Cu2O nanocubes with polyimine shells serving as diffusion barriers. The simple encapsulation with 50 nm thick shells significantly enhances the CH4-to-C2H4 ratio of Cu2O nanocatalysts from 0.14 to 8.9, achieving a Faradaic efficiency of 50.2% for CH4 at a partial current density of −201 mA cm–2 in alkaline electrolytes. In situ X-ray absorption and Raman spectroscopy demonstrate that encapsulation promotes the accumulation of surface-adsorbed hydroxide ions and significantly stabilized Cu(I) species throughout eCO2RR, with over 82% Cu(I) retention at −200 mA cm–2 for 2 h. Density functional theory calculations support the high coverage of surface-adsorbed hydroxide ions favored *CO hydrogenation over dimerization. This shell encapsulation strategy provides a straightforward approach to modulating eCO2RR mechanisms and product selectivity by tuning local chemical environments and Cu-oxidation states.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 3","pages":"2642–2653 2642–2653"},"PeriodicalIF":11.3,"publicationDate":"2025-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143259028","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

Tertiary Alcohols as Mechanistic Probes for Photocatalysis: the Gas-Phase Reaction of 2-Methyl-2-Pentanol on Titania P25 in a Microphotoreactor 作为光催化机理探针的叔醇：微光反应器中 2-甲基-2-戊醇在二氧化钛 P25 上的气相反应

IF 12.9 1区化学

ACS Catalysis Pub Date : 2025-01-28 DOI: 10.1021/acscatal.4c07001

Clara C. Aletsee, Paula Neumann, Ib Chorkendorff, Martin Tschurl, Ueli Heiz

{"title":"Tertiary Alcohols as Mechanistic Probes for Photocatalysis: the Gas-Phase Reaction of 2-Methyl-2-Pentanol on Titania P25 in a Microphotoreactor","authors":"Clara C. Aletsee, Paula Neumann, Ib Chorkendorff, Martin Tschurl, Ueli Heiz","doi":"10.1021/acscatal.4c07001","DOIUrl":"https://doi.org/10.1021/acscatal.4c07001","url":null,"abstract":"Despite intense research in heterogeneous photocatalysis, a lack of mechanistic understanding still hinders the rational design of efficient photocatalysts to make them competitive with thermal processes that currently dominate the industry. This study elucidates the underlying mechanism of photoreactions by employing tertiary alcohols as probe molecules on a titania P25 catalyst for the understanding of photocatalytic reactions on a molecular scale. We show that the reactions do not follow the commonly assumed reaction mechanism of separate but coupled redox reactions. Instead, the gas-phase reaction occurs selectively via a homolytic bond cleavage of the long alkyl chain, leading to the formation of the corresponding ketone and an alkane, as exemplified for 2-methyl-2-pentanol at ambient pressure. The alkane stems predominantly from the recombination of the alkyl-moiety with surface hydrogen. Additionally, we demonstrate that the alkyl moiety can also undergo a dimerization reaction forming a long chain alkane, which is facilitated on bare TiO2. The high time-resolution enabled by the used microreactor allowed us to confirm that this side reaction is a higher-order process, which is governed by the alcohol surface coverage on TiO2. The parallels of the observed reaction properties with studies performed on a TiO2(110) single crystal in vacuum reveal that no significant pressure and material gap exists. On the one hand, this strongly suggests that also the reaction mechanism for the conversion of other alcohols must be reconsidered on titania-based photocatalysts and, on the other hand, demonstrates the potential of tertiary alcohols as mechanistic probes in photocatalysis. Moreover, the highly selective reactions of tertiary alcohols may open up alternative routes for chemical synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"25 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055463","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

High-Efficiency Dual-Site Biomimetic Catalyst for Lignin Depolymerization

IF 11.3 1区化学

ACS Catalysis Pub Date : 2025-01-28 DOI: 10.1021/acscatal.4c0711310.1021/acscatal.4c07113

Wenzhi Jiang, Qifeng Li, Meifang Cao, Hongming Lou, Zhixian Li* and Xueqing Qiu*,

{"title":"High-Efficiency Dual-Site Biomimetic Catalyst for Lignin Depolymerization","authors":"Wenzhi Jiang, Qifeng Li, Meifang Cao, Hongming Lou, Zhixian Li* and Xueqing Qiu*, ","doi":"10.1021/acscatal.4c0711310.1021/acscatal.4c07113","DOIUrl":"https://doi.org/10.1021/acscatal.4c07113https://doi.org/10.1021/acscatal.4c07113","url":null,"abstract":"Developing biomimetic catalysts with enhanced catalytic efficiency is a promising strategy to address the challenges of lignin depolymerization under mild conditions. In this study, we designed a dual-site biomimetic catalyst, Pd@Ce-PZDC, engineered to emulate the lignin-degrading functions of natural laccase and peroxidase enzymes, thereby facilitated lignin depolymerization. The laccase-like activity of Pd@Ce-PZDC exhibited a catalytic efficiency (Vmax/Km) of 1.3 × 10–2 min–1, which is 3.14 times higher than that of natural laccase and 1.62 times greater than that of the single-site bioinspired laccase MOF catalyst Ce-PZDC. Its peroxidase-like activity, assessed with TMB and H2O2, is 5.6 and 11.2 times higher, respectively, than that of Ce-PZDC. Density Functional Theory (DFT) calculations indicated a synergistic dual-site effect where Pd NPs activate Ce(IV) within the MOF, imparting it with laccase-like activity akin to Ce(III), thereby increasing the number of active sites and enhancing overall catalytic efficiency. Under mild conditions (60 °C in aqueous solution), Pd@Ce-PZDC demonstrated high efficiency in the oxidative depolymerization of birch lignin, selectively cleaving β-O-4 and β–β linkages. This resulted in a reduction in molecular weight of lignin and produced aromatic monomers (approximately 13.0%), including vanillin, syringaldehyde, and vanillic acid. This dual-site synergistic strategy offers a promising avenue for valorization of lignin and the development of effective catalytic systems for biomass conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 3","pages":"2595–2606 2595–2606"},"PeriodicalIF":11.3,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258975","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