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High-Conductivity Lignin-Derived Carbon Fiber-Embedded CuFe2O4 Catalysts for Electrooxidation of HMF into FDCA 用于将 HMF 电氧化成 FDCA 的高导电性木质素衍生碳纤维嵌入式 CuFe2O4 催化剂
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-17 DOI: 10.1021/acscatal.4c0422710.1021/acscatal.4c04227
Haohan Wu, Bowen Liu, Yi Qi*, Xueqing Qiu, Liheng Chen* and Yanlin Qin*, 
{"title":"High-Conductivity Lignin-Derived Carbon Fiber-Embedded CuFe2O4 Catalysts for Electrooxidation of HMF into FDCA","authors":"Haohan Wu,&nbsp;Bowen Liu,&nbsp;Yi Qi*,&nbsp;Xueqing Qiu,&nbsp;Liheng Chen* and Yanlin Qin*,&nbsp;","doi":"10.1021/acscatal.4c0422710.1021/acscatal.4c04227","DOIUrl":"https://doi.org/10.1021/acscatal.4c04227https://doi.org/10.1021/acscatal.4c04227","url":null,"abstract":"<p >The electrocatalytic oxidation of 5-hydroxymethylfurfural (HMF) provides a viable pathway for the efficient utilization of biomass resources. However, designing and regulating the activity and selectivity of the corresponding electrocatalysts remain significant challenge. Spinel compounds show great potential as catalysts due to their adjustable electronic structures and notable catalytic properties, but their intrinsic low conductivity has limited their further application. Herein, a lignin-based carbon fiber (LCF) embedded CuFe<sub>2</sub>O<sub>4</sub> catalyst (CuFe<sub>2</sub>O<sub>4</sub>/LCF) is successfully constructed using an electrospinning technique. The catalyst can efficiently and selectively synthesize 2,5-furandicarboxylic acid (FDCA) at a relatively low potential. The experimental results and theoretical simulations demonstrate that the introduction of lignin can significantly optimize the pregraphitic turbine carbon microstructure of the carbon fibers and facilitate rapid electron transfer between CuFe<sub>2</sub>O<sub>4</sub> and the carbon layer. Furthermore, the A<sub>Td</sub>–O–B<sub>Oh</sub> interactions on the surface of the CuFe<sub>2</sub>O<sub>4</sub> spinel structure significantly enhance the adsorption capacity for the substrates and OH<sup>–</sup> species, effectively promoting the catalytic reaction. The findings hope to provide a unique perspective to improve the catalytic activity of lignin carbon fiber spinel catalysts and the stability of biomass value-added mechanism.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16127–16139 16127–16139"},"PeriodicalIF":11.3,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571129","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Catalytic Hydrogenolysis of Lignin into Propenyl-monophenol over Ru Single Atoms Supported on CeO2 with Rich Oxygen Vacancies 具有富氧空位的 CeO2 上支持的 Ru 单原子催化水解木质素生成丙烯基单苯酚
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-17 DOI: 10.1021/acscatal.4c0318410.1021/acscatal.4c03184
Kaili Zhang*, Jianchun Jiang*, Zhe Liu, Jun Ye, Ran Tao, Hao Xu, Jingcong Xie, Jing Yang, Jian Zhao, Ning Zhang and Kui Wang*, 
{"title":"Catalytic Hydrogenolysis of Lignin into Propenyl-monophenol over Ru Single Atoms Supported on CeO2 with Rich Oxygen Vacancies","authors":"Kaili Zhang*,&nbsp;Jianchun Jiang*,&nbsp;Zhe Liu,&nbsp;Jun Ye,&nbsp;Ran Tao,&nbsp;Hao Xu,&nbsp;Jingcong Xie,&nbsp;Jing Yang,&nbsp;Jian Zhao,&nbsp;Ning Zhang and Kui Wang*,&nbsp;","doi":"10.1021/acscatal.4c0318410.1021/acscatal.4c03184","DOIUrl":"https://doi.org/10.1021/acscatal.4c03184https://doi.org/10.1021/acscatal.4c03184","url":null,"abstract":"<p >Lignin is the most abundant aromatic source of natural products, but developing efficient catalysts to depolymerize it into valuable monophenol with high yield and unique selectivity remains a challenge. Herein, we report a Ru single-atom catalyst (SAC) supported on rod CeO<sub>2</sub> with oxygen vacancies (Ov) for the depolymerization of birch dioxane acidolysis lignin (DAL). A near-theoretical maximum monophenol yield (14.8 wt %) with good selectivity to 4-<i>n</i>-propenyl guaiacol (51.4%), as well as high catalyst stability, was achieved. The calculated turnover (TON) was 387 mol<sub>aromatics</sub>/mol<sub>Ru</sub>, which is 55× higher than that of the Ru/C catalyst. The possible reaction for this catalyst was proposed by studying a series of lignin model compounds and in situ DRIFT measurements. The mechanism involves the cleavage of C<sub>α</sub>–OH and C<sub>β</sub>–O bonds to produce coniferyl alcohol, followed by the removal of γ-OH to generate 4-<i>n</i>-propenyl guaiacol. The effects of some key parameters like solvent, Ru content, temperature, reaction time, and H<sub>2</sub> pressure were also investigated in terms of monophenol yields and average molecular weight. This work provides an economically feasible method for the depolymerization of lignin into highly valuable monophenols.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16115–16126 16115–16126"},"PeriodicalIF":11.3,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560458","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Modeling Dynamic Catalysis at ab Initio Accuracy: The Need for Free-Energy Calculation 以初始精度建立动态催化模型:自由能计算的必要性
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-17 DOI: 10.1021/acscatal.4c0537210.1021/acscatal.4c05372
Qi-Yuan Fan, Fu-Qiang Gong, Yun-Pei Liu, Hao-Xuan Zhu and Jun Cheng*, 
{"title":"Modeling Dynamic Catalysis at ab Initio Accuracy: The Need for Free-Energy Calculation","authors":"Qi-Yuan Fan,&nbsp;Fu-Qiang Gong,&nbsp;Yun-Pei Liu,&nbsp;Hao-Xuan Zhu and Jun Cheng*,&nbsp;","doi":"10.1021/acscatal.4c0537210.1021/acscatal.4c05372","DOIUrl":"https://doi.org/10.1021/acscatal.4c05372https://doi.org/10.1021/acscatal.4c05372","url":null,"abstract":"","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16086–16097 16086–16097"},"PeriodicalIF":11.3,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142571134","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Pore-Structure Engineering of Hierarchical β Zeolites for the Enhanced Hydrocracking of Waste Plastics to Liquid Fuels 用于将废塑料加氢裂化为液体燃料的分层 β 沸石孔隙结构工程研究
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-17 DOI: 10.1021/acscatal.4c0535410.1021/acscatal.4c05354
Muhammad Usman Azam, Auguste Fernandes, Maria João Ferreira, Waheed Afzal* and Inês Graça*, 
{"title":"Pore-Structure Engineering of Hierarchical β Zeolites for the Enhanced Hydrocracking of Waste Plastics to Liquid Fuels","authors":"Muhammad Usman Azam,&nbsp;Auguste Fernandes,&nbsp;Maria João Ferreira,&nbsp;Waheed Afzal* and Inês Graça*,&nbsp;","doi":"10.1021/acscatal.4c0535410.1021/acscatal.4c05354","DOIUrl":"https://doi.org/10.1021/acscatal.4c05354https://doi.org/10.1021/acscatal.4c05354","url":null,"abstract":"<p >Hydrocracking of plastics over bifunctional hierarchical zeolites is promising for the upcycling of plastics into value-added products. However, the exact role of their acidic and textural properties toward the catalytic activity remains unclear. Herein, we modified the structure of a β zeolite via dealumination and desilication routes, resulting in hierarchical zeolites. The parent and hierarchical modified β zeolite samples were loaded with Ni and studied for the hydrocracking of virgin HDPE. In comparison to the parent and dealuminated β zeolite, desilicated β zeolite showed a higher conversion of 87.8% with 66.7% of the products in the gasoline range, owing to its significantly high textural properties. The conversion and selectivity of gasoline-range hydrocarbons over the desilicated zeolite were further improved to 95.9 and 69.2%, respectively, by Ni addition. To unlock the structure–activity correlation of the various zeolite samples, the role of different activity-driven factors was studied, resulting in an empirical relationship that aligns with the observed conversions over different zeolite samples. Moreover, it was observed that it is possible to achieve high selectivity of iso-paraffins in gasoline-range hydrocarbons via the optimization of the balance between metal-acid sites on bifunctional hierarchical zeolites. Furthermore, both Ni-loaded hierarchical β zeolites showed good stability and the ability to be regenerated under cyclic runs. The best-performing Ni-loaded desilicated β zeolite was also maintained over various postconsumer waste plastics (conversion = 85–95%) and when using a mixture of postconsumer waste plastics (88.4%). A life cycle assessment and a comparison with the recent literature also demonstrated the advantages of the proposed hierarchical modification routes in achieving high gasoline productivity (6.6–7.6 g<sub>gasoline</sub>/g<sub>cat</sub>·h) and less environmental impact. Overall, these findings highlight the role of improved textural properties of noble-metal-free, easily modifiable, and environmentally friendly bifunctional hierarchical β zeolites for the enhanced conversion of waste plastics into liquid fuels.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16148–16165 16148–16165"},"PeriodicalIF":11.3,"publicationDate":"2024-10-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscatal.4c05354","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560491","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Oriented Conversion of HMF to FDCA under Mild Conditions over Lignin-Tailored Co Single-Atom Catalyst with Enhanced Co Loadings 在温和条件下,在木质素裁剪钴单原子催化剂上通过提高钴负载量定向转化 HMF 为 FDCA
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-16 DOI: 10.1021/acscatal.4c0441910.1021/acscatal.4c04419
Junkai Li, Guanhua Wang*, Xiaoyi Wang, Yutong Zhao, Yuze Zhao, Wenjie Sui, Dingsheng Wang and Chuanling Si*, 
{"title":"Oriented Conversion of HMF to FDCA under Mild Conditions over Lignin-Tailored Co Single-Atom Catalyst with Enhanced Co Loadings","authors":"Junkai Li,&nbsp;Guanhua Wang*,&nbsp;Xiaoyi Wang,&nbsp;Yutong Zhao,&nbsp;Yuze Zhao,&nbsp;Wenjie Sui,&nbsp;Dingsheng Wang and Chuanling Si*,&nbsp;","doi":"10.1021/acscatal.4c0441910.1021/acscatal.4c04419","DOIUrl":"https://doi.org/10.1021/acscatal.4c04419https://doi.org/10.1021/acscatal.4c04419","url":null,"abstract":"<p >Heterogeneous catalysis over single-atom catalysts (SACs) has garnered significant attention in biomass-derived platform chemical conversion owing to the high atomic utilization and reliable selectivity/stability. Herein, Co single-atom catalysts (Co–N/F1) derived from fractionated lignin were employed for the oriented oxidation of 5-hydroxymethylfurfural (HMF), a typical platform chemical derived from glucose, into 2,5-furandicarboxylicacid (FDCA) under mild conditions. The Co–N/F1 with enhanced Co content was obtained using the low-molecular-weight lignin fraction (F1) with high functional group contents (e.g., Ph–OH and COOH), and the as-prepared catalyst was demonstrated to present a Co–N<sub>4</sub> configuration. Owing to the absence of colored byproduct formation from HMF at elevated temperatures, Co–N/F1 realized the highly selective conversion of HMF to FDCA (100% HMF conversion, 99.20% FDCA yield) under mild conditions (65 °C, 3 bar O<sub>2</sub>), which outperformed most reported non-noble metal-supported catalysts. Density functional theory calculations indicate that the Co–N<sub>4</sub> site in Co–N/F1 facilitates the dehydrogenation of the α-C position on HMF and its aldehyde intermediates, resulting in a significantly enhanced catalytic efficiency. Furthermore, Co–N/F1 exhibited stable reusability due to the alkaline resistance of the Co–N<sub>4</sub> structure. Our study details the insights into the synthesis of Co-SACs using a lignin fractionation strategy and further demonstrates its good feasibility for the oriented conversion of biomass-derived platform chemicals under mild conditions.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16003–16013 16003–16013"},"PeriodicalIF":11.3,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Photoexcited Palladium-Catalyzed Synthesis of Chiral Allenes from Alkynes via Isomerization and Deracemization Sequence 光激发钯催化通过异构化和脱芳香化顺序从炔烃合成手性烯烃
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-16 DOI: 10.1021/acscatal.4c0495610.1021/acscatal.4c04956
Changhua Song,  and , Shouyun Yu*, 
{"title":"Photoexcited Palladium-Catalyzed Synthesis of Chiral Allenes from Alkynes via Isomerization and Deracemization Sequence","authors":"Changhua Song,&nbsp; and ,&nbsp;Shouyun Yu*,&nbsp;","doi":"10.1021/acscatal.4c0495610.1021/acscatal.4c04956","DOIUrl":"https://doi.org/10.1021/acscatal.4c04956https://doi.org/10.1021/acscatal.4c04956","url":null,"abstract":"<p >A photoexcited palladium-catalyzed synthesis of chiral allenes from alkynes via a sequence of isomerization and deracemization is disclosed. This method offers an efficient and cost-effective approach to produce a wide range of chiral allenes with good enantioselectivities and yields (up to 98% yield and 99% ee). The use of readily available and stable alkynes as starting materials simplifies experimental procedures and broadens the scope of the chiral allene synthesis. DBU plays a crucial dual role in this reaction to effectively facilitate the isomerization of alkynes to allenes and enhance the palladium-catalyzed deracemization under visible light excitation, both of which are vital for the success of the process.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"15997–16002 15997–16002"},"PeriodicalIF":11.3,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560398","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Nature’s Toolbox for the Hydrolysis of Lactams and Cyclic Imides 自然界水解内酰胺和环状酰亚胺的工具箱
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-16 DOI: 10.1021/acscatal.4c0447410.1021/acscatal.4c04474
Peter Stockinger,  and , Rebecca Buller*, 
{"title":"Nature’s Toolbox for the Hydrolysis of Lactams and Cyclic Imides","authors":"Peter Stockinger,&nbsp; and ,&nbsp;Rebecca Buller*,&nbsp;","doi":"10.1021/acscatal.4c0447410.1021/acscatal.4c04474","DOIUrl":"https://doi.org/10.1021/acscatal.4c04474https://doi.org/10.1021/acscatal.4c04474","url":null,"abstract":"<p >Hydrolytic enzymes, such as lactamases or hydantoinases, can be valuably applied to convert lactams (cyclic amides) and cyclic imides into optically pure compounds, for example, <span>d</span>- or <span>l</span>- amino acids, and to resolve racemic mixtures, such as Vince lactams. The chiral building blocks can be utilized to produce biologically active peptides, pesticides, sweeteners, and antibiotics, such as semisynthetic penicillins or cephalosporins. Furthermore, these compounds find application as feed and food additives and constitute useful intermediates for cosmetics, pharmaceuticals, or agrochemicals. Beyond their application in chemical synthesis, cyclic amide and imide hydrolyzing enzymes hold promise in the recovery of materials containing polyamides or in the bioremediation of antibiotics and herbicides. Today, lactam and cyclic imide hydrolyzing biocatalysts mainly originate from enzyme families associated with two distinct structural archetypes: (a) α/β-hydrolases (e.g., lipases) and (b) metal-dependent amidohydrolases (e.g., dihydropyrimidinases/hydantoinases). Beyond these well-explored sources, nature offers an additional wealth of mechanistically, catalytically, and structurally distinct enzymes for lactam and cyclic imide hydrolysis, including serine and metallo-β-lactamases, allantoinases, 5-oxoprolinases, and members of the amidase signature family. To facilitate the discovery of suitable biocatalysts for such types of hydrolysis reactions, we provide a comprehensive overview of application examples, as well as functional annotations (EC identifiers) and structural architectures (CATH identifiers), of the currently known biocatalytic toolbox. In addition, a protein sequence database containing all relevant biocatalyst superfamilies for cyclic amide and imide hydrolysis has been created (https://github.com/ccbiozhaw/CyclAmidImid).</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16055–16073 16055–16073"},"PeriodicalIF":11.3,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acscatal.4c04474","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560394","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Well-Defined Catalytic System for Integrating Homogeneous and Heterogeneous Catalysis 整合均相催化与异相催化的定义明确的催化系统
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-16 DOI: 10.1021/acscatal.4c0370110.1021/acscatal.4c03701
Hongli Wang, Jiashu Sun, Dongcheng He, Kang Zhao, Bo Qian and Feng Shi*, 
{"title":"Well-Defined Catalytic System for Integrating Homogeneous and Heterogeneous Catalysis","authors":"Hongli Wang,&nbsp;Jiashu Sun,&nbsp;Dongcheng He,&nbsp;Kang Zhao,&nbsp;Bo Qian and Feng Shi*,&nbsp;","doi":"10.1021/acscatal.4c0370110.1021/acscatal.4c03701","DOIUrl":"https://doi.org/10.1021/acscatal.4c03701https://doi.org/10.1021/acscatal.4c03701","url":null,"abstract":"<p >Catalysis is an eternal theme in chemical research because it is indispensable in the chemical industry. Homogeneous and heterogeneous catalysts possess their individual advantages and disadvantages, which are significantly complementary. Therefore, it is highly desirable to develop an effective and practical method for merging the benefits of homogeneous and heterogeneous catalysis. Recently, the application of organic ligands to modify heterogeneous supported catalysts has emerged as an important method to combine the advantages of heterogeneous catalysis with those of homogeneous catalysis. Ligands modified supported catalysts offer the potential to overcome major challenges in tunability and stability for supported catalysts. This Viewpoint discusses the recent progress in the synthesis and application of ligand modified supported metal catalysts in organic reactions that merge the advantages of homo- and heterogeneous catalysis. We discuss the preparation and characterization, the origin of enhanced activities, and the structure–activity relationship of ligand modified supported metal catalysts. The challenges and perspectives for future progress in this field will be given. This viewpoint provides important insights into the development of well-defined heterogeneous catalysts for integrating homogeneous and heterogeneous catalysis.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16025–16043 16025–16043"},"PeriodicalIF":11.3,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560408","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
A van der Waals–Covalent Bonding-Inspired Typical Coordination with Ultrahigh Lattice Mismatch as Active Sites for Hydrogen Electrosynthesis 范德华-共价键激发的典型配位与超高晶格错配可作为氢电合成的活性位点
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-16 DOI: 10.1021/acscatal.4c0404610.1021/acscatal.4c04046
Xinying Luo, Junjie Xiong, Xiaolong Liu, Zhichang Xiao*, Qinghua Zhang, Yuchen Cai, Bowen Liu, Yang Gao, Tao Liang, Qiang Zheng, Jichen Dong*, Ting Tan*, Zhenxing Wang, Yunqi Liu and Bin Wang*, 
{"title":"A van der Waals–Covalent Bonding-Inspired Typical Coordination with Ultrahigh Lattice Mismatch as Active Sites for Hydrogen Electrosynthesis","authors":"Xinying Luo,&nbsp;Junjie Xiong,&nbsp;Xiaolong Liu,&nbsp;Zhichang Xiao*,&nbsp;Qinghua Zhang,&nbsp;Yuchen Cai,&nbsp;Bowen Liu,&nbsp;Yang Gao,&nbsp;Tao Liang,&nbsp;Qiang Zheng,&nbsp;Jichen Dong*,&nbsp;Ting Tan*,&nbsp;Zhenxing Wang,&nbsp;Yunqi Liu and Bin Wang*,&nbsp;","doi":"10.1021/acscatal.4c0404610.1021/acscatal.4c04046","DOIUrl":"https://doi.org/10.1021/acscatal.4c04046https://doi.org/10.1021/acscatal.4c04046","url":null,"abstract":"<p >We report a van der Waals–covalent bonding interface with boosted hydrogen evolution reaction (HER) catalytic activity compared to the well-known edge defects for two-dimensional catalysts. The central region of a chemical-vapor-deposition-grown multilayer MoS<sub>2</sub> is transformed to Mo<sub>5</sub>N<sub>6</sub>, thus forming a van der Waals–covalent (v–c) interface that has high structural strain due to the large lattice mismatch of 10.5% between the two different phases. The large structural distortion creates several kinds of stretched sites that show ideal HER catalytic activities theoretically, such as the S sites coordinated by 2 Mo atoms and the 3-coordinated N atoms. In experiments, the v–c interface bonding and coordination variations were observed, and a number-of-layers-dependent MoS<sub>2</sub>-to-Mo<sub>5</sub>N<sub>6</sub> transformation mechanism was found. Using the on-chip electrochemical micromeasurements, the catalytic activity of the atoms at the v–c interface was demonstrated to be higher than the edge atoms of either MoS<sub>2</sub> or Mo<sub>5</sub>N<sub>6</sub> sheets. Further macrotests using the as-synthesized powder materials showed greatly enhanced HER performance of the v–c structure than MoS<sub>2</sub> or Mo<sub>5</sub>N<sub>6</sub> sheets. This comprehensive study of the v–c structure shows the synthesis route and a clear bonding interface, establishes the number-of-layers-dependent transformation principles, exhibits high-priority HER activities, and explains the strain/coordination-variation-induced catalytic mechanism.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16074–16085 16074–16085"},"PeriodicalIF":11.3,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
引用次数: 0
Selective Association Enforced by the Confinement Effect To Boost the Regioselectivity of Vinyl Acetate Hydroformylation 利用封闭效应加强选择性结合,提高醋酸乙烯酯加氢甲酰化的区域选择性
IF 11.3 2区 生物学
ACS Chemical Biology Pub Date : 2024-10-16 DOI: 10.1021/acscatal.4c0393210.1021/acscatal.4c03932
Guoqing Wang, Miao Jiang, Benhan Fan, Zhao Sun, Leilei Qian, Guangjun Ji, Lei Ma, Cunyao Li, Zhaozhan Wang, Guifa Long*, Yong Yang*, Li Yan* and Yunjie Ding*, 
{"title":"Selective Association Enforced by the Confinement Effect To Boost the Regioselectivity of Vinyl Acetate Hydroformylation","authors":"Guoqing Wang,&nbsp;Miao Jiang,&nbsp;Benhan Fan,&nbsp;Zhao Sun,&nbsp;Leilei Qian,&nbsp;Guangjun Ji,&nbsp;Lei Ma,&nbsp;Cunyao Li,&nbsp;Zhaozhan Wang,&nbsp;Guifa Long*,&nbsp;Yong Yang*,&nbsp;Li Yan* and Yunjie Ding*,&nbsp;","doi":"10.1021/acscatal.4c0393210.1021/acscatal.4c03932","DOIUrl":"https://doi.org/10.1021/acscatal.4c03932https://doi.org/10.1021/acscatal.4c03932","url":null,"abstract":"<p >1,3-Propanediol derived from vinyl acetate through hydroformylation/hydrogenation has always been considered the most promising strategy to substitute the current technology. So far, the linear aldehyde regioselectivity of vinyl acetate hydroformylation is still far from satisfactory. Herein, we prepare a series of single-site catalysts with a confinement effect, in which different second-shell atoms (C, O, and N) are bonded with the P atom. The Rh–P–N-POPs catalyst, in which two N and one O atoms are bonded with a P atom, delivers not only a good aldehyde yield but also attractive regioselectivity (l/b = 1.5), outperforming Rh–P–C-POPs (l/b = 0.007), Rh–P–O-POPs (l/b = 0.01), and all previously reported optimizing Rh catalysts (l/b = 0.8). Characterizations and DFT calculations suggest that the enhanced performance is mainly ascribed to selective association enforced by the confinement effect and electron-deficient properties. The confinement effect, which is imposed by the ligand, hinders the chelating effect of acetate and facilitates the selective association of Rh with the terminal carbon of olefins. Meanwhile, N as second-shell atoms in the Rh–P–N-POPs catalyst endows Rh active sites with an electron-deficient coordination environment and accelerates the linear aldehyde forming rate. This work offers an effective strategy to regulate the hydroformylation performance by the confinement effect for the modulation of a second-shell atom, which sheds light on designing heterogeneous catalysts with high regioselectivity for the hydroformylation of functional olefins.</p>","PeriodicalId":11,"journal":{"name":"ACS Chemical Biology","volume":"14 21","pages":"16014–16024 16014–16024"},"PeriodicalIF":11.3,"publicationDate":"2024-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142560393","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"生物学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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