Pub Date : 2026-02-27DOI: 10.1016/j.chempr.2025.102918
Simon Stampe Kildahl, Clemens Kaussler, Ruth Ebenbauer, Thomas Balle Bech, Riccardo Giovanelli, Martin Lahn Henriksen, Mansurali Mithani, Ilke Uysal-Unalan, Dennis Wilkens Juhl, Niels Chr. Nielsen, Troels Skrydstrup
Here, we report the transition metal-catalyzed hydrogenation or combined hydrocyanation/hydrogenation of abundant but difficult-to-recycle consumer nitrile and styrene-butadiene-styrene rubbers to generate non-porous solid amine adsorbents that capture and release CO2 by thermal swing adsorption. The protocol is showcased with real-life samples such as nitrile gloves. Despite being non-porous, the rubber-derived amine materials display excellent and fast CO2 adsorption of up to an average capacity of 3.05 mmol/g when subjected to simulated flue gas at 90°C. Furthermore, the materials are shown to be complementary to the state-of-the-art solid adsorbent, Calgary Framework 20 (CALF-20), which is less effective at this temperature. We anticipate that our work will provide a potential pathway forward to rapidly accessing new solid adsorbents from consumer rubbers for managing CO2 emissions.
{"title":"CO2 capture with post-modified nitrile and styrene-butadiene-styrene rubbers","authors":"Simon Stampe Kildahl, Clemens Kaussler, Ruth Ebenbauer, Thomas Balle Bech, Riccardo Giovanelli, Martin Lahn Henriksen, Mansurali Mithani, Ilke Uysal-Unalan, Dennis Wilkens Juhl, Niels Chr. Nielsen, Troels Skrydstrup","doi":"10.1016/j.chempr.2025.102918","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102918","url":null,"abstract":"Here, we report the transition metal-catalyzed hydrogenation or combined hydrocyanation/hydrogenation of abundant but difficult-to-recycle consumer nitrile and styrene-butadiene-styrene rubbers to generate non-porous solid amine adsorbents that capture and release CO<sub>2</sub> by thermal swing adsorption. The protocol is showcased with real-life samples such as nitrile gloves. Despite being non-porous, the rubber-derived amine materials display excellent and fast CO<sub>2</sub> adsorption of up to an average capacity of 3.05 mmol/g when subjected to simulated flue gas at 90°C. Furthermore, the materials are shown to be complementary to the state-of-the-art solid adsorbent, Calgary Framework 20 (CALF-20), which is less effective at this temperature. We anticipate that our work will provide a potential pathway forward to rapidly accessing new solid adsorbents from consumer rubbers for managing CO<sub>2</sub> emissions.","PeriodicalId":268,"journal":{"name":"Chem","volume":"26 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319826","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}
Aqueous zinc-iodine batteries (AZIBs) are attractive for safe and low-cost energy storage yet are hindered by sluggish iodine redox kinetics and severe polyiodide shuttling. While single-atom catalysts (SACs) based on d-block transition metals have been extensively explored, their limited orbital directionality constrains performance. Herein, we propose an orbital-engineering strategy using p-block elements to enable effective p-p orbital hybridization and enhanced electronic coupling. Bi SACs anchored on N-doped porous carbons (Bi-NC) leverage their semi-metallic nature to induce effective Bi 6p-I 5p interactions, thereby accelerating iodine conversion and suppressing shuttling. The Bi-NC/I2 cathode delivers 134.7 mAh g−1 with exceptional stability over 100,000 cycles at 16 A g−1, exhibiting only 0.000141% decay per cycle. Furthermore, a Zn/Bi-NC/I2 pouch cell achieves 1.07 mAh cm−2 and maintains 100% capacity retention after 200 cycles at 5 mA cm−2. This work establishes p-p orbital hybridization as a powerful design principle for durable aqueous batteries.
锌-碘水溶液电池（azib）是一种安全、低成本的储能技术，但其存在碘氧化还原动力学缓慢和多碘离子穿梭严重的问题。虽然基于d-嵌段过渡金属的单原子催化剂（SACs）已经被广泛探索，但其有限的轨道方向性限制了其性能。在此，我们提出了一种轨道工程策略，使用p块元素来实现有效的p-p轨道杂化和增强电子耦合。锚定在n掺杂多孔碳（Bi- nc）上的Bi SACs利用其半金属性质诱导有效的Bi 6p-I 5p相互作用，从而加速碘转化并抑制穿梭。Bi-NC/I2阴极提供134.7 mAh g - 1，在16 A g - 1下超过100,000次循环具有出色的稳定性，每个循环仅显示0.000141%的衰减。此外，Zn/Bi-NC/I2袋电池达到1.07 mAh cm - 2，并在5 mA cm - 2下循环200次后保持100%的容量保留。这项工作确立了p-p轨道杂化作为耐用水性电池的有力设计原则。
{"title":"p-p orbital hybridization enables durable aqueous zinc-iodine batteries","authors":"Ying Wang, Yanqing Fu, Qiliang Wei, Dongjiang Yang, Qiao Liu, Weiyou Yang","doi":"10.1016/j.chempr.2025.102911","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102911","url":null,"abstract":"Aqueous zinc-iodine batteries (AZIBs) are attractive for safe and low-cost energy storage yet are hindered by sluggish iodine redox kinetics and severe polyiodide shuttling. While single-atom catalysts (SACs) based on <em>d</em>-block transition metals have been extensively explored, their limited orbital directionality constrains performance. Herein, we propose an orbital-engineering strategy using <em>p</em>-block elements to enable effective <em>p</em>-<em>p</em> orbital hybridization and enhanced electronic coupling. Bi SACs anchored on N-doped porous carbons (Bi-NC) leverage their semi-metallic nature to induce effective Bi 6<em>p</em>-I 5<em>p</em> interactions, thereby accelerating iodine conversion and suppressing shuttling. The Bi-NC/I<sub>2</sub> cathode delivers 134.7 mAh g<sup>−1</sup> with exceptional stability over 100,000 cycles at 16 A g<sup>−1</sup>, exhibiting only 0.000141% decay per cycle. Furthermore, a Zn/Bi-NC/I<sub>2</sub> pouch cell achieves 1.07 mAh cm<sup>−2</sup> and maintains 100% capacity retention after 200 cycles at 5 mA cm<sup>−2</sup>. This work establishes <em>p</em>-<em>p</em> orbital hybridization as a powerful design principle for durable aqueous batteries.","PeriodicalId":268,"journal":{"name":"Chem","volume":"25 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319828","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}
Pub Date : 2026-02-25DOI: 10.1016/j.chempr.2025.102921
Madeleine A. Gaidimas, Jiaru Bai, Yeonghun Kang, Kent O. Kirlikovali, Varinia Bernales, Alán Aspuru-Guzik, Omar K. Farha
The traditional development of novel metal-organic frameworks (MOFs) is often hindered by challenges such as synthetic accessibility and time- and resource-intensive experimentation. High-throughput, automated experimental and computational techniques have enabled rapid chemical space exploration and theoretical MOF design. When combined with artificial intelligence (AI), these methods can be used to lead autonomous laboratories to new frontiers for MOF discovery, where these materials can be designed for a specific application, efficiently synthesized, characterized, and evaluated. This perspective highlights the role of AI in advancing automated MOF synthesis and characterization, computational MOF design and screening, and the integration of these approaches within autonomous workflows to ultimately enable the MOF laboratories of the future.
{"title":"Reimagining metal-organic framework discovery: Integrating experiment, computation, and artificial intelligence","authors":"Madeleine A. Gaidimas, Jiaru Bai, Yeonghun Kang, Kent O. Kirlikovali, Varinia Bernales, Alán Aspuru-Guzik, Omar K. Farha","doi":"10.1016/j.chempr.2025.102921","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102921","url":null,"abstract":"The traditional development of novel metal-organic frameworks (MOFs) is often hindered by challenges such as synthetic accessibility and time- and resource-intensive experimentation. High-throughput, automated experimental and computational techniques have enabled rapid chemical space exploration and theoretical MOF design. When combined with artificial intelligence (AI), these methods can be used to lead autonomous laboratories to new frontiers for MOF discovery, where these materials can be designed for a specific application, efficiently synthesized, characterized, and evaluated. This perspective highlights the role of AI in advancing automated MOF synthesis and characterization, computational MOF design and screening, and the integration of these approaches within autonomous workflows to ultimately enable the MOF laboratories of the future.","PeriodicalId":268,"journal":{"name":"Chem","volume":"25 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147319829","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}
Pub Date : 2026-02-18DOI: 10.1016/j.chempr.2025.102904
Zachariah Lockhart, Mihai V. Popescu, Juan V. Alegre-Requena, Jay Ahuja, Shaokang Chai, Robert S. Paton, Martin D. Smith
The transition from radical to ionic reactivity is a key design feature of many photochemical reactions, enabling complex transformations not possible under either mechanistic regime alone. Ground-state alkenes are common substrates in existing methods of this type, serving as radical acceptors to generate open-shell intermediates from which the radical–polar crossover (RPC) event is oxidatively or reductively triggered by a photocatalyst. Here, we describe an alternative RPC mechanism proceeding via an alkene triplet diradical. In this transformation, an iodine radical liberated during a homolytic aromatic substitution step functions as a single-electron oxidant to generate an iminium electrophile that can be intercepted en route to complex natural-product-like amines. An enantioselective variant of the reaction, enabled by an oxidatively installed sulfinyl leaving group, points to the generality of this underdeveloped pattern of diradical reactivity, paving the way for other triplet-state reactions that incorporate both one- and two-electron bond-forming processes.
{"title":"A radical–polar crossover approach to complex nitrogen heterocycles via the triplet state","authors":"Zachariah Lockhart, Mihai V. Popescu, Juan V. Alegre-Requena, Jay Ahuja, Shaokang Chai, Robert S. Paton, Martin D. Smith","doi":"10.1016/j.chempr.2025.102904","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102904","url":null,"abstract":"The transition from radical to ionic reactivity is a key design feature of many photochemical reactions, enabling complex transformations not possible under either mechanistic regime alone. Ground-state alkenes are common substrates in existing methods of this type, serving as radical acceptors to generate open-shell intermediates from which the radical–polar crossover (RPC) event is oxidatively or reductively triggered by a photocatalyst. Here, we describe an alternative RPC mechanism proceeding via an alkene triplet diradical. In this transformation, an iodine radical liberated during a homolytic aromatic substitution step functions as a single-electron oxidant to generate an iminium electrophile that can be intercepted en route to complex natural-product-like amines. An enantioselective variant of the reaction, enabled by an oxidatively installed sulfinyl leaving group, points to the generality of this underdeveloped pattern of diradical reactivity, paving the way for other triplet-state reactions that incorporate both one- and two-electron bond-forming processes.","PeriodicalId":268,"journal":{"name":"Chem","volume":"22 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146208792","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}
Pub Date : 2026-02-17DOI: 10.1016/j.chempr.2025.102905
Longfei Liu, Dezhi Chen, Huixin Yan, Yihao Zhang, Xinkui Wang, Min Wang
Catalytic reactions that rely only on ultraviolet-visible (UV-vis) light for photothermal conversion are usually insufficient, as they neglect the infrared portion of sunlight. Here, we constructed an efficient photothermal platform by coordinating high-density Co single sites with nitrogen atoms in a donor-acceptor porous organic polymer. The introduction of Co sites enhances infrared light absorption and significantly improves photothermal conversion ability. Moreover, under full-spectrum illumination, the catalyst can cooperatively utilize UV-vis and infrared (IR) light. While UV-vis light generates charge carriers, the local heating effect from IR light promotes charge migration and proton transfer, leading to an excellent CO production rate of 44.43 mmol⋅g−1⋅h−1. This work demonstrates one of the best performances among organic catalysts for photothermal CO2 hydrogenation and opens new possibilities for designing efficient organic photothermal systems.
{"title":"A donor-acceptor porous organic polymer anchoring a high density of cobalt single sites realizes full-spectrum photothermal CO2 hydrogenation","authors":"Longfei Liu, Dezhi Chen, Huixin Yan, Yihao Zhang, Xinkui Wang, Min Wang","doi":"10.1016/j.chempr.2025.102905","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102905","url":null,"abstract":"Catalytic reactions that rely only on ultraviolet-visible (UV-vis) light for photothermal conversion are usually insufficient, as they neglect the infrared portion of sunlight. Here, we constructed an efficient photothermal platform by coordinating high-density Co single sites with nitrogen atoms in a donor-acceptor porous organic polymer. The introduction of Co sites enhances infrared light absorption and significantly improves photothermal conversion ability. Moreover, under full-spectrum illumination, the catalyst can cooperatively utilize UV-vis and infrared (IR) light. While UV-vis light generates charge carriers, the local heating effect from IR light promotes charge migration and proton transfer, leading to an excellent CO production rate of 44.43 mmol⋅g<sup>−1</sup>⋅h<sup>−1</sup>. This work demonstrates one of the best performances among organic catalysts for photothermal CO<sub>2</sub> hydrogenation and opens new possibilities for designing efficient organic photothermal systems.","PeriodicalId":268,"journal":{"name":"Chem","volume":"319 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146223052","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}
Pub Date : 2026-02-16DOI: 10.1016/j.chempr.2025.102906
Xiao Wei, Fan Ding, Jia Li, Guohua Li, Liqiang Zhang, Wangxiao He, Wenjia Liu
Programmable autonomy is central to nanorobotics, yet most molecular devices depend on enzyme cascades, gene circuits, or external fields for decision-making. We present TriCAN (tri-phasic cell-adaptive nanorobot), a single-peptide molecular robot that implements a closed-loop sense-compute-actuate cycle solely through reversible phase transitions. TriCAN contains three covalently linked domains: a mesenchymal stem cell (MSC)-homing sensor, a histidine-methionine pentamer processor that converts acidic pH and reactive-oxygen stress into gel-to-condensate-to-solution transitions, and a bone morphogenetic protein (BMP)-peptide effector that is sterically caged until the final phase. The processor executes an analog “enable” gate on MSC contact, a dual-input AND gate on acidic pH and reactive oxygen species (ROS), and a time-delay gate set by condensate dissolution kinetics. This phase-transition logic enables fully enzyme-free computation, requires no external power, and fits into a molecular footprint. In rodent models of chronic and diabetic periodontitis, TriCAN remained dormant in healthy sites yet restored osteogenesis and regenerated alveolar bone without ectopic ossification or toxicity.
{"title":"TriCAN: A phase-transition molecular robot realizing closed-loop sense-compute-actuate control for inflammation-triggered bone regeneration","authors":"Xiao Wei, Fan Ding, Jia Li, Guohua Li, Liqiang Zhang, Wangxiao He, Wenjia Liu","doi":"10.1016/j.chempr.2025.102906","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102906","url":null,"abstract":"Programmable autonomy is central to nanorobotics, yet most molecular devices depend on enzyme cascades, gene circuits, or external fields for decision-making. We present TriCAN (tri-phasic cell-adaptive nanorobot), a single-peptide molecular robot that implements a closed-loop sense-compute-actuate cycle solely through reversible phase transitions. TriCAN contains three covalently linked domains: a mesenchymal stem cell (MSC)-homing sensor, a histidine-methionine pentamer processor that converts acidic pH and reactive-oxygen stress into gel-to-condensate-to-solution transitions, and a bone morphogenetic protein (BMP)-peptide effector that is sterically caged until the final phase. The processor executes an analog “enable” gate on MSC contact, a dual-input AND gate on acidic pH and reactive oxygen species (ROS), and a time-delay gate set by condensate dissolution kinetics. This phase-transition logic enables fully enzyme-free computation, requires no external power, and fits into a molecular footprint. In rodent models of chronic and diabetic periodontitis, TriCAN remained dormant in healthy sites yet restored osteogenesis and regenerated alveolar bone without ectopic ossification or toxicity.","PeriodicalId":268,"journal":{"name":"Chem","volume":"18 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2026-02-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146198909","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}
Pub Date : 2026-02-12Epub Date: 2025-08-28DOI: 10.1016/j.chempr.2025.102720
Ping Qin , Junjun Liu , Miao Zhang , Lin Yang , Xiaoyan Zhong , Guangjie Xia , Chengshuo Shen , Huibin Qiu , Zhifeng Huang
Directing the symmetry breaking of a pair of enantiomers is one of the significant topics in modern chemistry, leading to the generation of enantiomerically enriched molecules through kinetic resolution or asymmetric synthesis. It is challenging to direct dynamic kinetic resolution (DKR) when enantiomers have small racemization barriers, such as helical polycyclic arenes (HPAs). Herein, the reliable control of DKR of nitrogen (N)-doped HPAs is demonstrated on inorganic surfaces composed of chiral topographies at the atomic scale. Through the formation of non-covalent N-inorganic bonds, HPAs enantiospecifically adsorb onto the left-handed and right-handed inorganic surfaces to break symmetry and then generate the homochiral M- and P-configuration supramolecular aggregates, respectively. Such symmetry-breaking manipulation can generally be adapted to inorganic materials exhibiting high surface energy, such as silica, titanium oxides, iron oxides, tin oxides, and gold. This work introduces a general principle to direct DKR of enantiomers with small racemization barriers, providing an insight into understanding the mysterious origins of homochirality.
{"title":"Dynamic kinetic resolution of helical polycyclic arenes directed at inorganic chiral surfaces deposited via substrate rotation","authors":"Ping Qin , Junjun Liu , Miao Zhang , Lin Yang , Xiaoyan Zhong , Guangjie Xia , Chengshuo Shen , Huibin Qiu , Zhifeng Huang","doi":"10.1016/j.chempr.2025.102720","DOIUrl":"10.1016/j.chempr.2025.102720","url":null,"abstract":"<div><div>Directing the symmetry breaking of a pair of enantiomers is one of the significant topics in modern chemistry, leading to the generation of enantiomerically enriched molecules through kinetic resolution or asymmetric synthesis. It is challenging to direct dynamic kinetic resolution (DKR) when enantiomers have small racemization barriers, such as helical polycyclic arenes (HPAs). Herein, the reliable control of DKR of nitrogen (N)-doped HPAs is demonstrated on inorganic surfaces composed of chiral topographies at the atomic scale. Through the formation of non-covalent N-inorganic bonds, HPAs enantiospecifically adsorb onto the left-handed and right-handed inorganic surfaces to break symmetry and then generate the homochiral <em>M</em>- and <em>P</em>-configuration supramolecular aggregates, respectively. Such symmetry-breaking manipulation can generally be adapted to inorganic materials exhibiting high surface energy, such as silica, titanium oxides, iron oxides, tin oxides, and gold. This work introduces a general principle to direct DKR of enantiomers with small racemization barriers, providing an insight into understanding the mysterious origins of homochirality.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 2","pages":"Article 102720"},"PeriodicalIF":19.6,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911186","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}
Solar-driven catalytic transformation of plastic waste into valuable products is an attractive strategy to mitigate adverse environmental impacts of waste accumulation and contribute to sustainable manufacturing. A crucial step in advancing this technology is to harness solar energy and boost “waste-to-value” conversion via appropriate reaction systems and high-performance catalysts. Despite continued efforts, catalytic system design and photo-induced reaction mechanisms for complex molecular conversion remain to be settled. This review analyzes reaction systems in state-of-the-art solar-driven plastic conversion, classified by catalyst-plastic interaction modes: solid-solid, liquid-solid, and liquid-liquid. It discusses relevant approaches, including photocatalysis, photoelectrocatalysis, and photothermal catalysis. Additionally, we evaluate the fundamental processes (i.e., photon absorption, charge carrier utilization, and surface/interface catalytic reactions) in different reaction systems and discuss the intrinsic solar-to-chemical conversion from a photophysical/chemical perspective. Finally, we present a range of design strategies for reaction systems and catalysts to raise reaction efficiency and the overall economics of solar-driven plastic conversion.
{"title":"Solar-to-chemical conversion in catalytic plastic transformation","authors":"Shuai Zhang , Xintong Gao , Meijun Guo , Jingrun Ran , Shi-Zhang Qiao","doi":"10.1016/j.chempr.2025.102789","DOIUrl":"10.1016/j.chempr.2025.102789","url":null,"abstract":"<div><div>Solar-driven catalytic transformation of plastic waste into valuable products is an attractive strategy to mitigate adverse environmental impacts of waste accumulation and contribute to sustainable manufacturing. A crucial step in advancing this technology is to harness solar energy and boost “waste-to-value” conversion via appropriate reaction systems and high-performance catalysts. Despite continued efforts, catalytic system design and photo-induced reaction mechanisms for complex molecular conversion remain to be settled. This review analyzes reaction systems in state-of-the-art solar-driven plastic conversion, classified by catalyst-plastic interaction modes: solid-solid, liquid-solid, and liquid-liquid. It discusses relevant approaches, including photocatalysis, photoelectrocatalysis, and photothermal catalysis. Additionally, we evaluate the fundamental processes (i.e., photon absorption, charge carrier utilization, and surface/interface catalytic reactions) in different reaction systems and discuss the intrinsic solar-to-chemical conversion from a photophysical/chemical perspective. Finally, we present a range of design strategies for reaction systems and catalysts to raise reaction efficiency and the overall economics of solar-driven plastic conversion.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 2","pages":"Article 102789"},"PeriodicalIF":19.6,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145383771","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}
Pub Date : 2026-02-12Epub Date: 2025-08-12DOI: 10.1016/j.chempr.2025.102697
Xiaoling Zhang , Wei Ran , Jiefang Sun , Shiwei Li , Wenxiao Pan , Xinyu Li , Jingfu Liu , Rui Liu , Guibin Jiang
Correlating the physical structure of reactive sites with catalysis is key to designing atomically precise heterogeneous catalysts. However, understanding the structural features of the various active sites at the nanoparticle level is vital for establishing a structure-activity relationship because multiple and unquantifiable reactive sites co-exist on these catalysts. Here, we analyzed the surface-enhanced Raman spectroscopy (SERS) spectra of chemisorbed probe, 4-iodo-2,6-dimethylphenylisocyanide, to obtain the site distribution of Pd sites on Au@Pd catalysts. Based on the new SERS-derived structure and distribution of Pd sites, the performance of Au@Pd in hydrogenation of nitroaromatics is directly correlated with the theoretical site-specific activity and selectivity. This fully understood structure-activity relationship allows accurate prediction of the performance of different catalysts. We enriched the most active and selective single-atom Pd sites on the Au surface with an Ag monolayer, reaching >99% conversion of 4-chloronitrobenzene into 4-chloroaniline with >99% selectivity during a 100-h continuous-flow reaction.
{"title":"Opening the structure-activity relationship black box in Pd-catalyzed nitroaromatic hydrogenation by quantifying reactive sites of Au@Pd catalysts","authors":"Xiaoling Zhang , Wei Ran , Jiefang Sun , Shiwei Li , Wenxiao Pan , Xinyu Li , Jingfu Liu , Rui Liu , Guibin Jiang","doi":"10.1016/j.chempr.2025.102697","DOIUrl":"10.1016/j.chempr.2025.102697","url":null,"abstract":"<div><div>Correlating the physical structure of reactive sites with catalysis is key to designing atomically precise heterogeneous catalysts. However, understanding the structural features of the various active sites at the nanoparticle level is vital for establishing a structure-activity relationship because multiple and unquantifiable reactive sites co-exist on these catalysts. Here, we analyzed the surface-enhanced Raman spectroscopy (SERS) spectra of chemisorbed probe, 4-iodo-2,6-dimethylphenylisocyanide, to obtain the site distribution of Pd sites on Au@Pd catalysts. Based on the new SERS-derived structure and distribution of Pd sites, the performance of Au@Pd in hydrogenation of nitroaromatics is directly correlated with the theoretical site-specific activity and selectivity. This fully understood structure-activity relationship allows accurate prediction of the performance of different catalysts. We enriched the most active and selective single-atom Pd sites on the Au surface with an Ag monolayer, reaching >99% conversion of 4-chloronitrobenzene into 4-chloroaniline with >99% selectivity during a 100-h continuous-flow reaction.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 2","pages":"Article 102697"},"PeriodicalIF":19.6,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144819694","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}
Pub Date : 2026-02-12Epub Date: 2025-10-07DOI: 10.1016/j.chempr.2025.102751
Swati Jindal , Kuntal Pal , Mostafa Zeama , Partha Maity , Tian Jin , Mickaele Bonneau , Rajesh Kancherla , Omar F. Mohammed , Osama Shekhah , Magnus Rueping , Mohamed Eddaoudi
This work reports the design and synthesis of a novel imine-linked 2D covalent organic framework (COF), TPDA-BiPy-COF, constructed from [3,3′-bipyridine]-6,6′-dicarboxaldehyde (3,3′-BiPy) as an electron acceptor and tetrakis(4-aminophenyl)-1,4-phenylenediamine (TPDA) as a donor. The COF features pyridyl-imine linkages, i.e., Nimine-Ni-Nbipyridine, with active nitrogen sites that facilitate proton reduction to hydrogen. To improve photocatalytic hydrogen evolution performance, Ni(II) centers were introduced via post-synthetic metalation, forming TPDA-BiPy@NiX₂ COF (X = Cl, Br). The coordination of Ni(II) with the imine and bipyridine nitrogen atoms enhanced framework planarity and conjugation, thereby boosting photocatalytic activity. Notably, TPDA-BiPy@Ni(II) COF achieved an excellent hydrogen evolution rate of 34.13 mmol g⁻¹ h⁻¹ under visible light, without requiring a cocatalyst. Furthermore, the metallaphotoredox activity of TPDA-BiPy@Ni(II) displayed its promise for photocatalyzed C–S cross-coupling reaction. This dual-functional catalyst highlights the advantage of incorporating nickel into COFs, offering a cost-effective and sustainable alternative to noble-metal-based systems for photocatalysis and synthetic transformations.
{"title":"Nickel-embedded covalent organic frameworks for dual photocatalytic hydrogen evolution and cross-coupling catalysis","authors":"Swati Jindal , Kuntal Pal , Mostafa Zeama , Partha Maity , Tian Jin , Mickaele Bonneau , Rajesh Kancherla , Omar F. Mohammed , Osama Shekhah , Magnus Rueping , Mohamed Eddaoudi","doi":"10.1016/j.chempr.2025.102751","DOIUrl":"10.1016/j.chempr.2025.102751","url":null,"abstract":"<div><div>This work reports the design and synthesis of a novel imine-linked 2D covalent organic framework (COF), <strong>TPDA-BiPy-COF</strong>, constructed from [3,3′-bipyridine]-6,6′-dicarboxaldehyde (3,3′-<strong>BiPy</strong>) as an electron acceptor and tetrakis(4-aminophenyl)-1,4-phenylenediamine (<strong>TPDA</strong>) as a donor. The COF features pyridyl-imine linkages, i.e., N<sub>imine</sub>-Ni-N<sub>bipyridine</sub>, with active nitrogen sites that facilitate proton reduction to hydrogen. To improve photocatalytic hydrogen evolution performance, Ni(II) centers were introduced via post-synthetic metalation, forming <strong>TPDA-BiPy@NiX₂</strong> COF (X = Cl, Br). The coordination of Ni(II) with the imine and bipyridine nitrogen atoms enhanced framework planarity and conjugation, thereby boosting photocatalytic activity. Notably, <strong>TPDA-BiPy@Ni(II)</strong> COF achieved an excellent hydrogen evolution rate of 34.13 mmol g⁻¹ h⁻¹ under visible light, without requiring a cocatalyst. Furthermore, the metallaphotoredox activity of TPDA-BiPy@Ni(II) displayed its promise for photocatalyzed C–S cross-coupling reaction. This dual-functional catalyst highlights the advantage of incorporating nickel into COFs, offering a cost-effective and sustainable alternative to noble-metal-based systems for photocatalysis and synthetic transformations.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 2","pages":"Article 102751"},"PeriodicalIF":19.6,"publicationDate":"2026-02-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145241673","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：