Chemical Society Reviews最新文献

{"title":"Synthesis of Xenes: physical and chemical methods","authors":"Alessandro Molle, Junji Yuhara, Yukiko Yamada-Takamura and Zdenek Sofer","doi":"10.1039/D4CS00999A","DOIUrl":"10.1039/D4CS00999A","url":null,"abstract":"<p >Since the debut of silicene in the experimental stage more than a decade ago, the family of two-dimensional elementary layers beyond graphene, called Xenes or transgraphenes, has rapidly expanded to include elements from groups II to VI of the periodic table. This expansion has opened pathways for the engineering of elementary monolayers that are inherently different from their bulk counterparts in terms of fundamental physical properties. Common guidelines for synthesizing Xenes can be categorized into well-defined methodological approaches. On the one hand, bottom-up methods, such as physical epitaxial methods, enable the growth of monolayers, multilayers, and heterostructured Xenes. On the other hand, top-down chemical methods, including topotactic deintercalation and liquid-phase exfoliation, are gaining prominence due to the possibility of massive production. This review provides an extensive view of the currently available synthesis routes for Xenes, highlighting the full range of Xenes reported to date, along with the most relevant identification techniques.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 4","pages":" 1845-1869"},"PeriodicalIF":40.4,"publicationDate":"2025-01-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cs/d4cs00999a?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020800","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Optimizing photocatalysis <i>via</i> electron spin control.","authors":"Shaoxiong He, Yanxi Chen, Jingyun Fang, Yijiang Liu, Zhiqun Lin","doi":"10.1039/d4cs00317a","DOIUrl":"https://doi.org/10.1039/d4cs00317a","url":null,"abstract":"<p><p>Solar-driven photocatalytic technology holds significant potential for addressing energy crisis and mitigating global warming, yet is limited by light absorption, charge separation, and surface reaction kinetics. The past several years has witnessed remarkable progress in optimizing photocatalysis <i>via</i> electron spin control. This approach enhances light absorption through energy band tuning, promotes charge separation by spin polarization, and improves surface reaction kinetics <i>via</i> strengthening surface interaction and increasing product selectivity. Nevertheless, the lack of a comprehensive and critical review on this topic is noteworthy. Herein, we provide a summary of the fundamentals of electron spin control and the techniques employed to scrutinize the electron spin state of active sites in photocatalysts. Subsequently, we highlight advanced strategies for manipulating electron spin, including doping design, defect engineering, magnetic field regulation, metal coordination modulation, chiral-induced spin selectivity, and combined strategies. Additionally, we review electron spin control-optimized photocatalytic processes, including photocatalytic water splitting, CO₂ reduction, pollutant degradation, and N₂ fixation, providing specific examples and detailed discussion on underlying mechanisms. Finally, we outline perspectives on further enhancing photocatalytic activity through electron spin manipulation. This review seeks to offer valuable insights to guide future research on electron spin control for improving photocatalytic applications.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" ","pages":""},"PeriodicalIF":40.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996502","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}

{"title":"Unified approaches in transition metal catalyzed C(sp3)–H functionalization: recent advances and mechanistic aspects","authors":"Jagrit Grover, Amal Tom Sebastian, Siddhartha Maiti, Alex C. Bissember and Debabrata Maiti","doi":"10.1039/D0CS00488J","DOIUrl":"10.1039/D0CS00488J","url":null,"abstract":"<p >In organic synthesis, C(sp<small>³</small>)–H functionalization is a revolutionary method that allows direct alteration of unactivated C–H bonds. It can obviate the need for pre-functionalization and provides access to streamlined and atom economical routes for the synthesis of complex molecules starting from simple starting materials. Many strategies have evolved, such as photoredox catalysis, organocatalysis, non-directed C–H activation, transiently directed C–H activation, and native functionality directed C–H activation. Together these advances have reinforced the importance of C(sp<small>³</small>)–H functionalization in synthetic chemistry. C(sp<small>³</small>)–H functionalization has direct applications in pharmacology, agrochemicals, and materials science, demonstrating its ability to transform synthetic approaches by creating new retrosynthetic disconnections and boost the efficiency of chemical processes. This review aims to provide an overview of current state of C(sp<small>³</small>)–H functionalization, focusing more on recent breakthroughs and associated mechanistic insights.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 4","pages":" 2006-2053"},"PeriodicalIF":40.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996503","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}

{"title":"Covalent organic frameworks as superior adsorbents for the removal of toxic substances","authors":"Yubo Li, Jinxia Wei, Jian Wang, Yuanyuan Wang, Peishuang Yu, Yao Chen, Zhenjie Zhang","doi":"10.1039/d4cs00591k","DOIUrl":"https://doi.org/10.1039/d4cs00591k","url":null,"abstract":"Developing new materials capable of the safe and efficient removal of toxic substances has become a research hotspot in the field of materials science, as these toxic substances pose a serious threat to human health, both directly and indirectly. Covalent organic frameworks (COFs), as an emerging class of crystalline porous materials, have advantages such as large specific surface area, tunable pore size, designable structure, and good biocompatibility, which have been proven to be a superior adsorbent design platform for toxic substances capture. This review will summarize the synthesis methods of COFs and the properties and characteristics of typical toxicants, discuss the design strategies of COF-based adsorbents for the removal of toxic substances, and highlight the recent advancements in COF-based adsorbents as robust candidates for the efficient removal of various types of toxicants, such as animal toxins, microbial toxins, phytotoxins, environmental toxins, <em>etc.</em> The adsorption performance and related mechanisms of COF-based adsorbents for different types of toxic substances will be discussed. The complex host–guest interactions mainly include electrostatic, π–π interactions, hydrogen bonding, hydrophobic interactions, and molecular sieving effects. In addition, the adsorption performance of various COF-based adsorbents will be compared, and strategies such as reasonable adjustment of pore size, introduction of functionalities, and preparation of composite materials can effectively improve the adsorption efficiency of toxins. Finally, we also point out the challenges and future development directions that COFs may face in the field of toxicant removal. It is expected that this review will provide valuable insights into the application of COF-based adsorbents in the removal of toxicants and the development of new materials.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":"18 1","pages":""},"PeriodicalIF":46.2,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143020804","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}

{"title":"Chiral-at-metal catalysts: history, terminology, design, synthesis, and applications","authors":"Lilu Zhang and Eric Meggers","doi":"10.1039/D4CS01043D","DOIUrl":"10.1039/D4CS01043D","url":null,"abstract":"<p >For decades, advances in chiral transition metal catalysis have been closely tied to the development of customized chiral ligands. Recently, however, an alternative approach to this traditional metal-plus-chiral-ligand method has emerged. In this new strategy, chiral transition metal catalysts are composed entirely of achiral ligands, with the overall chirality originating exclusively from a stereogenic metal center. This “chiral-at-metal” approach offers the benefit of structural simplicity. More importantly, by removing the need for chiral elements within the ligand framework, it opens up new possibilities for designing innovative catalyst architectures with unique properties. As a result, chiral-at-metal catalysis is becoming an increasingly important area of research. This review offers a comprehensive overview and detailed insights into asymmetric chiral-at-metal catalysis, encouraging scientists to explore new avenues in asymmetric transition metal catalysis and driving innovation in both fundamental and applied research.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 4","pages":" 1986-2005"},"PeriodicalIF":40.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cs/d4cs01043d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990921","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Radical Brook rearrangement: past, present, and future","authors":"Yunxiao Zhang, Gang Zhou, Shanshan Liu and Xiao Shen","doi":"10.1039/D4CS01275E","DOIUrl":"10.1039/D4CS01275E","url":null,"abstract":"<p >The Brook rearrangement has emerged as one of the most pivotal transformations in organic chemistry, with broad applications spanning organic synthesis, drug design, and materials science. Since its discovery in the 1950s, the anion-mediated Brook rearrangement has been extensively studied, laying the groundwork for the development of numerous innovative reactions. In contrast, the radical Brook rearrangement has garnered comparatively less attention, primarily due to the challenges associated with the controlled generation of alkoxyl radicals under mild conditions. However, recent advancements in visible-light catalysis and transition-metal catalysis have positioned the radical Brook rearrangement as a promising alternative synthetic strategy in organic synthesis. Despite these developments, significant limitations and challenges remain, warranting further investigation. This review provides an overview of the radical Brook rearrangement, tracing its development from past to present, and offers perspectives on future directions in the field to inspire the creation of novel synthetic tools based on this transformation.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 4","pages":" 1870-1904"},"PeriodicalIF":40.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990971","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}

{"title":"Correction: From photocatalysis to photon–phonon co-driven catalysis for methanol reforming to hydrogen and valuable by-products","authors":"Hui Wang, Eleana Harkou, Achilleas Constantinou, Sultan M. Al-Salem, George Manos, Junwang Tang","doi":"10.1039/d5cs90005k","DOIUrl":"https://doi.org/10.1039/d5cs90005k","url":null,"abstract":"Correction for ‘From photocatalysis to photon–phonon co-driven catalysis for methanol reforming to hydrogen and valuable by-products’ by Hui Wang <em>et al.</em>, <em>Chem. Soc. Rev.</em>, 2025, https://doi.org/10.1039/d4cs00551a.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":"30 1","pages":""},"PeriodicalIF":46.2,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990972","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}

{"title":"Affinity descriptor of metal catalysts: concept, measurement and application of oxygen affinity in the catalytic transformation of oxygenates","authors":"Huixiang Li, Zhipeng Huang, Chaofeng Zhang, Yehong Wang, Xiaoqiang Zhang, Changhui Liang and Z. Conrad Zhang","doi":"10.1039/D4CS00472H","DOIUrl":"10.1039/D4CS00472H","url":null,"abstract":"<p >Multiple oxygenate groups in biomass-based feedstocks are open to multiple catalytic pathways and products, typically resulting in low selectivity for the desired products. In this context, strategies for rational catalyst design are critical to obtain high selectivity for the desired products in biomass upgrading. The Sabatier principle provides a conceptual framework for designing optimal catalysts by following the volcanic relationship between catalyst activity for a reaction and the binding strength of a substrate on a catalyst. The affinity descriptor of catalysts, which scales the interaction strength of the functional groups of substrates with catalysts, can potentially be developed to correlate with catalyst performance in reactions. Specifically, the oxygen affinity of catalysts, as a measure of the interaction strength between oxygenates and catalysts, can be applied to rationalize the oxygenate transformation and guide the rational design of efficient catalysts based on the Sabatier principle. This review highlights the fundamental basis and applications of affinity descriptors in catalysis, with a focus on the oxygen affinity of catalysts for the transformation of biomass-derived oxygenate compounds.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 4","pages":" 1905-1923"},"PeriodicalIF":40.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142996501","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}

{"title":"High power output density organic thermoelectric devices for practical applications in waste heat harvesting","authors":"Xin Hao, Jing Wang and Hong Wang","doi":"10.1039/D4CS01045K","DOIUrl":"10.1039/D4CS01045K","url":null,"abstract":"<p >Organic thermoelectric (TE) materials are of great interest for researchers in waste heat recovery, especially for waste heat harvesting at near room temperature. Significant progress has been achieved in terms of their figure of merit (<em>zT</em>) values recently, which has presented new insights into the development of organic TE materials. For numerous practical applications of thermoelectric generators, where waste heat is unlimited and cost negligible, the primary goal has been switched to achieve high power output density rather than improving their heat-to-electricity conversion efficiency. In this review, we first discussed the theoretical relationship between the thermoelectric properties of organic materials and the power output density of devices. Then, we analyzed the state-of-the-art strategies for improving the power factor of organic materials. Methods for modulating the structure of the TE legs were discussed with an aim to maintain the temperature difference between the hot side and the cold side of the devices. Finally, some representative devices were summarized for the potential applications of the TEGs along with an outlook on the future of organic thermoelectric materials and devices.</p>","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":" 4","pages":" 1957-1985"},"PeriodicalIF":40.4,"publicationDate":"2025-01-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142990155","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}

{"title":"Selectivity control by zeolites during methanol-mediated CO2 hydrogenation processes","authors":"Tangkang Liu, Zhiyao Liu, Shican Jiang, Peng Peng, Zhiqiang Liu, Abhishek Dutta Chowdhury, Guoliang Liu","doi":"10.1039/d4cs01042f","DOIUrl":"https://doi.org/10.1039/d4cs01042f","url":null,"abstract":"The thermocatalytic conversion of CO<small>₂</small> with green or blue hydrogen into valuable energy and commodity chemicals such as alcohols, olefins, and aromatics emerges as one of the most promising strategies for mitigating global warming concerns in the future. This process can follow either a CO<small>₂</small>-modified Fischer–Tropsch synthesis route or a methanol-mediated route, with the latter being favored for its high product selectivity beyond the Anderson–Schulz–Flory distribution. Despite the progress of the CO<small>₂</small>-led methanol-mediated route over bifunctional metal/zeolite catalysts, challenges persist in developing catalysts with both high activity and selectivity due to the complexity of CO<small>₂</small> hydrogenation reaction networks and the difficulty in controlling C–O bond activation and C–C bond coupling on multiple active sites within zeolites. Moreover, the different construction and proximity modes of bifunctionality involving redox-based metallic sites and acidic zeolite sites have been explored, which have not been systematically reviewed to derive reliable structure–reactivity relationships. To bridge this “knowledge gap”, in this review, we will provide a comprehensive and critical overview of contemporary research on zeolite-confined metal catalysts for alcohol synthesis and zeolite-based bifunctional tandem/cascade catalytic systems for C<small>₂₊</small> hydrocarbons synthesis in CO<small>₂</small> hydrogenation <em>via</em> the methanol-mediated route. Accordingly, special emphasis will be placed on evaluating how confinement and proximity effects within the “redox-acid” bifunctional systems influence the reaction outcomes, particularly regarding product selectivity, which has also been analyzed from the mechanistic standpoint. This review will also examine the synergistic interactions among various catalyst components that govern catalysis, offering valuable insights for the rational design of new or improved catalyst systems. By discussing current challenges and recognizing future opportunities in CO<small>₂</small> hydrogenation using zeolite-based bifunctional catalysis, this review aims to contribute to the advancement of sustainable and efficient processes for CO<small>₂</small> valorization.","PeriodicalId":68,"journal":{"name":"Chemical Society Reviews","volume":"44 1","pages":""},"PeriodicalIF":46.2,"publicationDate":"2025-01-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142988376","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}