ACS Catalysis 最新文献

Initiation of the Phillips Cr(VI) Catalyst by Alkenes 烯类对菲利普斯 Cr(VI) 催化剂的引发作用

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-27 DOI: 10.1021/acscatal.4c04326

Masud M. Monwar, Jared L. Barr, Kathy S. Clear, Carlos A. Cruz, Mitchell Refvik, Max P. McDaniel

{"title":"Initiation of the Phillips Cr(VI) Catalyst by Alkenes","authors":"Masud M. Monwar, Jared L. Barr, Kathy S. Clear, Carlos A. Cruz, Mitchell Refvik, Max P. McDaniel","doi":"10.1021/acscatal.4c04326","DOIUrl":"https://doi.org/10.1021/acscatal.4c04326","url":null,"abstract":"As part of a continuing effort to better understand the initiation (i.e., the reduction and self-alkylation) of the Phillips commercial Cr(VI)/silica catalyst, this study attempted to isotopically label the initiating group on the starting PE chain. The hexavalent catalyst was reduced by deuterated olefin (C2D4 or C3D6), then polymerization of C2H4 was conducted. This amplified the starting group signal during the subsequent 2H NMR analysis of the polymer. In a second method, the Cr(VI) catalyst was reduced by various olefins, then hydrolyzed by injection of protic liquids. Redox products were then analyzed by GC–MS. These data indicate that the initial chain made on a Cr(VI) site begins with a methyl group. No unsaturation was observed. In addition, oxygen was found in many of the resultant chains, apparently incorporated from the original Cr(VI) as part of the initiation process. It demonstrates that reduction and alkylation are not necessarily separate and independent reactions, but often occur in a concerted process. It further suggests that there is not one initiation mechanism, but many, depending on the reactivity of the individual sites and the monomer used.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325592","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

Retraction of “Pd-Partially Reduced Graphene Oxide Catalysts (Pd/PRGO): Laser Synthesis of Pd Nanoparticles Supported on PRGO Nanosheets for Carbon–Carbon Cross Coupling Reactions” 撤回 "Pd-部分还原氧化石墨烯催化剂（Pd/PRGO）：激光合成支撑在 PRGO 纳米片上的钯纳米颗粒，用于碳-碳交叉偶联反应"

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-27 DOI: 10.1021/acscatal.4c04278

Sherif Moussa, Ali R. Siamaki, B. Frank Gupton, M. Samy El-Shall

引用次数: 0

Nonmetal Plasmon-Induced Carrier Backflow and Prolonged Lifetime for CO2 Photoreduction 非金属等离子体诱导的载流子回流和延长的二氧化碳光还原寿命

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-27 DOI: 10.1021/acscatal.4c04644

Peiyu Hu, Jianjun Zhang, Guijie Liang, Jiaguo Yu, Feiyan Xu

{"title":"Nonmetal Plasmon-Induced Carrier Backflow and Prolonged Lifetime for CO2 Photoreduction","authors":"Peiyu Hu, Jianjun Zhang, Guijie Liang, Jiaguo Yu, Feiyan Xu","doi":"10.1021/acscatal.4c04644","DOIUrl":"https://doi.org/10.1021/acscatal.4c04644","url":null,"abstract":"Constructing traditional heterojunctions involving noble metal cocatalysts is a well-established strategy for boosting photocatalytic efficiency by separating electron/hole pairs and improving light absorption through localized surface plasmon resonance (LSPR) effects. However, the high cost and limited availability of noble metals constrain their application, while the impact of plasmon effects on charge carrier dynamics and lifetimes, crucial for regulating photocatalytic performance, has been overlooked. Here, we propose integrating graphitic carbon dots (CDs) as proficient nonmetal cocatalysts into SnO2 nanofibers to facilitate high-efficiency photoreactions. Under light irradiation, photoelectrons within the SnO2 migrate to the CDs driven by the bent bands and the internal electric field, alongside inherent free electrons, stimulating into high-energy excited electrons due to LSPR effects. These energized electrons subsequently backflow to the SnO2 for stabilization, initiating a cyclic process that effectively prolongs carrier lifetimes within the SnO2/CDs nanohybrids, as confirmed by femtosecond transient absorption spectroscopy. Synergizing with enhanced optical absorption and CO2 chemisorption facilitated by the CDs, the resulting SnO2/CDs nanofibers demonstrate improved CO2 photoreduction performance.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325593","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

Unveiling Plasmon-Induced Suzuki–Miyaura Reactions on Silver Nanoparticles via Raman Spectroscopy 通过拉曼光谱揭示银纳米粒子上的等离子体诱导的铃木-宫浦反应

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-27 DOI: 10.1021/acscatal.4c04578

Yunjia Wei, Dexiang Chen, Xingce Fan, Xiao Tang, Lei Yao, Xing Zhao, Qiang Li, Jiawei Wang, Teng Qiu, Qi Hao

{"title":"Unveiling Plasmon-Induced Suzuki–Miyaura Reactions on Silver Nanoparticles via Raman Spectroscopy","authors":"Yunjia Wei, Dexiang Chen, Xingce Fan, Xiao Tang, Lei Yao, Xing Zhao, Qiang Li, Jiawei Wang, Teng Qiu, Qi Hao","doi":"10.1021/acscatal.4c04578","DOIUrl":"https://doi.org/10.1021/acscatal.4c04578","url":null,"abstract":"The Suzuki–Miyaura coupling reaction is an efficient organic method for synthesizing biphenyl products. However, its conventional reliance on toxic soluble organometallic palladium catalysts or expensive palladium nanoparticles, along with the need for elevated temperatures and prolonged reaction times, presents a significant challenge. Herein, we demonstrate a palladium-free approach using plasmonic silver nanoparticles that enables the Suzuki–Miyaura coupling reaction to proceed at room temperature under visible light. Utilizing the surface-enhanced Raman scattering characteristics of silver, we conducted dynamic self-monitoring of the reaction. Our findings reveal that this plasmon-induced Suzuki–Miyaura coupling reaction fundamentally operates as a heterogeneous reaction involving coupling between radicals, distinct from conventional palladium-based reactions. Moreover, the cleavage of C–Cl and C–B bonds, fundamental prerequisite to the coupling, is driven by plasmonic hot electrons and plasmon-induced reactive oxygen species, respectively. These findings not only provide insights into the design and regulation of plasmonic catalysts but also enhance theoretical understanding of the Suzuki–Miyaura reaction in a broader context.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325594","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

Multi-Band Centre Co-Tailoring of Iridium Diphosphide Nanoclusters Motivating Industrial Current Density Hydrogen Production 二磷化铱纳米团簇的多波段中心共定制技术促进工业电流密度制氢

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-27 DOI: 10.1021/acscatal.4c04561

Xuan-Yi Zhu, Shui-Zhong Zhao, Xue-Feng Zhang, Xia Huang, Cheng-Juan Gao, Li-Hong Yu, Zi-Yi Du, Li-Ming Cao, Chun-Ting He

{"title":"Multi-Band Centre Co-Tailoring of Iridium Diphosphide Nanoclusters Motivating Industrial Current Density Hydrogen Production","authors":"Xuan-Yi Zhu, Shui-Zhong Zhao, Xue-Feng Zhang, Xia Huang, Cheng-Juan Gao, Li-Hong Yu, Zi-Yi Du, Li-Ming Cao, Chun-Ting He","doi":"10.1021/acscatal.4c04561","DOIUrl":"https://doi.org/10.1021/acscatal.4c04561","url":null,"abstract":"Transition metal phosphides (TMPs) are high-potential catalysts for hydrogen evolution reaction (HER) yet struggle with the long-term maintenance of high activity at ampere-level current densities. Size cutting and heteroatom modification of TMPs are effective ways to improve their surface affinities and catalytic efficiencies, but the particle stabilities and synergistic regulation of band structures at different sites have become huge challenges. Herein, we have successfully synthesized cluster-level sulfur-doped iridium diphosphide (S-IrP2) through a molecular engineering strategy. It requires only low overpotentials of 133.6 ± 1.2 and 217.2 ± 2.6 mV to drive industrial current densities of 1.0 and 2.0 A·cm–2, respectively, being one of the best alkaline HER catalyst. Moreover, it showed almost no activity loss over 20,000 cycles and exhibited a remarkable charge transfer amount that exceeds those of reported TMPs. The electronic tailoring of IrP2 by sulfur atoms enables simultaneous shifting of the d-band and f-band centers of Ir and the p-band center of P, which co-optimizes the H and OH adsorption to lowering the H migration and H2 formation barriers. This work demonstrates that the molecular confinement synthesis holds tremendous prospects for architecting ultrafine metallic compounds with re-definable active surfaces.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325595","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

Photo-Induced Pyridylic C(sp3)–H Alkylation with Unactivated Alkenes Enabled by Hydrogen Atom Transfer/Lewis Acid Cocatalysis 通过氢原子转移/刘易斯酸催化与未活化烯烃发生光诱导吡啶C(sp3)-H烷基化反应

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-27 DOI: 10.1021/acscatal.4c05026

Yusuke Kuroda, Hikaru Saito, Tsukasa Tawatari, Kiyosei Takasu

引用次数: 0

Direct Deoxygenative Homocoupling of Alcohols to Access C(sp3)–C(sp3) Bonds via Synergistic Ruthenium/Nickel Catalysis 通过钌/镍协同催化使醇直接脱氧同偶联以获得 C(sp3)-C(sp3)键

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-25 DOI: 10.1021/acscatal.4c04400

Dawei Cao, Shumei Xia, Li-Juan Li, Huiying Zeng, Chao-Jun Li

{"title":"Direct Deoxygenative Homocoupling of Alcohols to Access C(sp3)–C(sp3) Bonds via Synergistic Ruthenium/Nickel Catalysis","authors":"Dawei Cao, Shumei Xia, Li-Juan Li, Huiying Zeng, Chao-Jun Li","doi":"10.1021/acscatal.4c04400","DOIUrl":"https://doi.org/10.1021/acscatal.4c04400","url":null,"abstract":"With an ever-increasing emphasis on green synthesis of chemicals, there has been growing interest in deoxygenative conversion of alcohols as widely available organic feedstocks for chemical synthesis. However, the effective construction of the C(sp3)–C(sp3) bond via the direct homocoupling of simple alcohols is still challenging, due to the involvement of multistep reaction processes. Herein, we propose a general strategy for the direct deoxygenative coupling of alcohols via the synergetic catalysis of earth-abundant nickel and ruthenium, using hydrazine as a mediator. This protocol features the in situ formation of carbonyl intermediates via Ru-catalyzed alcohol dehydrogenation, followed by deoxygenative homocoupling to construct the C(sp3)–C(sp3) bond under Ni catalysis. The successful C(sp3)-O bond cleavage of alcohol does not require a hydrogen acceptor, and only environmentally friendly byproducts (nitrogen, hydrogen, and water) are generated. The method is particularly effective for benzyl alcohols with broad substrate scope and for late-stage elaborations of complex biological molecules, exemplifying the efficiency and practicability of the system.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142321070","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

Bench-Stable Low-Valent Chromium Catalysts for Hydrogenation of CO2, Bicarbonate, and Inorganic Carbonates to Formate 将二氧化碳、碳酸氢盐和无机碳酸盐加氢转化为甲酸酯的台式稳定低价铬催化剂

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-25 DOI: 10.1021/acscatal.4c04492

Tushar Singh, Akash Gutal, Anitta Regina, Amitava Banerjee, Manikandan Paranjothy, Subrata Chakraborty

{"title":"Bench-Stable Low-Valent Chromium Catalysts for Hydrogenation of CO2, Bicarbonate, and Inorganic Carbonates to Formate","authors":"Tushar Singh, Akash Gutal, Anitta Regina, Amitava Banerjee, Manikandan Paranjothy, Subrata Chakraborty","doi":"10.1021/acscatal.4c04492","DOIUrl":"https://doi.org/10.1021/acscatal.4c04492","url":null,"abstract":"Catalytic hydrogenation of the potent greenhouse gas carbon dioxide to obtain value-added products represents a much sought after methodology in academia and industry. Hydrogenation of CO2 to formic acid catalyzed by molecular complexes is a highly desirable protocol because of the industrial importance of formic acid and its potential application as a renewable hydrogen storage material. Herein we disclose that the bench-stable, low-valent phosphine-tethered chromium carbonyl complex Cr(DPPP)(CO)4 (C-3) (DPPP = 1,3-bis(diphenylphosphino)propane) catalyzed efficient hydrogenation of CO2 to formate giving a maximum turnover number (TON) of 259,000 at 130 °C in THF/H2O mixture after 24 h at the expense of 40 bar (CO2:H2 = 10:30) pressure. Biologically relevant sodium bicarbonate and inorganic carbonates were also tested for hydrogenation to sodium formate, furnishing decent yields of the desired products. Mechanistic investigation along with theoretical studies revealed that the reaction proceeded via the formation of a metallacarboxylate intermediate, which was further converted to a formato complex via an anionic hydrido carbonyl intermediate.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142325057","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

Reductive Olefin Bicyclo[1.1.0]butane Coupling Enabled by Iron Hydride Hydrogen Atom Transfer 通过氢化铁氢原子转移实现还原性烯烃双环[1.1.0]丁烷偶联

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-25 DOI: 10.1021/acscatal.4c04837

Guang Chen, Dayu Tian, Xiaocheng Wang, Hai-Jun Zhang

引用次数: 0

Strengthened Delocalized Electronic Effect in Nano-Nickel@Carbon with High Pyrrolic Nitrogen for Selective Hydrogenation of Substituted Nitrobenzene Hydrogenation 具有高吡咯烷酮氮的纳米镍@碳中用于取代硝基苯选择性加氢的强化去局域电子效应

IF 12.9 1区化学

ACS Catalysis Pub Date : 2024-09-25 DOI: 10.1021/acscatal.4c03995

Yongyue Yao, Chunyu Yin, Wei He, Yebin Zhou, Chaofan Ma, Yi Liu, Xiaonian Li, Chunshan Lu

{"title":"Strengthened Delocalized Electronic Effect in Nano-Nickel@Carbon with High Pyrrolic Nitrogen for Selective Hydrogenation of Substituted Nitrobenzene Hydrogenation","authors":"Yongyue Yao, Chunyu Yin, Wei He, Yebin Zhou, Chaofan Ma, Yi Liu, Xiaonian Li, Chunshan Lu","doi":"10.1021/acscatal.4c03995","DOIUrl":"https://doi.org/10.1021/acscatal.4c03995","url":null,"abstract":"Carbon-encapsulated metal (CEM) catalysts reconfigure the active site of the catalytic reaction by shifting from the conventional metal to the surface of the carbon material. Carbon-encapsulated structure has attracted wide attention in the fields of electrochemistry, thermal catalysis and photocatalysis. Herein, a nitrogen-doped carbon-encapsulated nickel catalyst was synthesized via hydrothermal synthesis, with pyrrolic N (NPyr) content accounting for 48.4% of the total nitrogen species. Experiments and density functional theory calculations reveal that the five-membered pyrrole ring shares six π electrons, and its electron cloud density on the carbon surface surpasses that of benzene or pyridine ring, promoting extensive electronic interaction between NPyrC and nickel. The interaction also extends beyond the vicinity of the doping sites and permeates throughout the entire carbon shell, thereby augmenting a greater number of potential active sites on the NC layer. This strengthened delocalized electronic effect imparts specificity in the adsorption and dissociation processes of hydrogen and p-chloronitrobenzene, leading to enhanced catalytic performance in the hydrogenation production of p-chloroaniline. The precise preparation of NPyr-doped CEM catalysts demonstrates its huge potential for industrial applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":null,"pages":null},"PeriodicalIF":12.9,"publicationDate":"2024-09-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142317401","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