Pub Date : 2025-12-11DOI: 10.1016/j.chempr.2025.102825
Morgan Cordell , Andrei K. Yudin
In this perspective, we introduce the concept of isoreactivity—a framework for identifying structural modules that sustain a forward reaction path. By emphasizing functional roles within mechanisms, rather than electron count or frontier orbital similarity, isoreactivity captures parallels that elude existing classifications. We illustrate how this approach describes established trends in reactivity and points toward novel transformations. We hope that codifying isoreactivity will open new avenues for discovery, offering chemists an intuitive and pedagogically clear principle for guiding reaction design.
{"title":"Isoreactivity in chemistry","authors":"Morgan Cordell , Andrei K. Yudin","doi":"10.1016/j.chempr.2025.102825","DOIUrl":"10.1016/j.chempr.2025.102825","url":null,"abstract":"<div><div>In this perspective, we introduce the concept of isoreactivity—a framework for identifying structural modules that sustain a forward reaction path. By emphasizing functional roles within mechanisms, rather than electron count or frontier orbital similarity, isoreactivity captures parallels that elude existing classifications. We illustrate how this approach describes established trends in reactivity and points toward novel transformations. We hope that codifying isoreactivity will open new avenues for discovery, offering chemists an intuitive and pedagogically clear principle for guiding reaction design.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102825"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145600131","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102665
Justin O.P. Waters , Elnaz Jamalzade , Hussein T. Abdulrazzaq , Nathaniel Kuch , Sampath R. Gunukula , James A. Dumesic , Philip J. Kersten , Thomas J. Schwartz
Many pharmaceuticals include chiral centers, which are introduced using high-cost building blocks such as (S)-3-hydroxy-γ-butyrolactone, (S)-HBL. This species is used in the synthesis of many important drugs, including statins, antibiotics, and HIV inhibitors, and it is currently produced from fossil resources via a high-cost, high-emission process. Here, we show that a nearly quantitative yield of enantiopure (S)-HBL can be obtained from glucose at ambient temperature, using a combination of biological and chemical catalysis. Whole-cell enzyme catalysis converts glucose to a labile intermediate (denoted as trione) that is subsequently reacted to (S)-HBL by metal-free homogeneous acid/base catalysis. These reactions do not involve the C5 of glucose, leading to enantiopure (S)-HBL, produced at less than half the present cost. This approach can also be used to produce other commercially important building blocks from sustainable feedstocks: the enzymes used for trione production are active in converting xylose, leading to the acrylate co-monomer 3-hydroxypropionic acid.
{"title":"Production of biorenewable, enantiopure (S)-3-hydroxy-γ-butyrolactone for pharmaceutical applications","authors":"Justin O.P. Waters , Elnaz Jamalzade , Hussein T. Abdulrazzaq , Nathaniel Kuch , Sampath R. Gunukula , James A. Dumesic , Philip J. Kersten , Thomas J. Schwartz","doi":"10.1016/j.chempr.2025.102665","DOIUrl":"10.1016/j.chempr.2025.102665","url":null,"abstract":"<div><div>Many pharmaceuticals include chiral centers, which are introduced using high-cost building blocks such as (S)-3-hydroxy-γ-butyrolactone, (S)-HBL. This species is used in the synthesis of many important drugs, including statins, antibiotics, and HIV inhibitors, and it is currently produced from fossil resources via a high-cost, high-emission process. Here, we show that a nearly quantitative yield of enantiopure (S)-HBL can be obtained from glucose at ambient temperature, using a combination of biological and chemical catalysis. Whole-cell enzyme catalysis converts glucose to a labile intermediate (denoted as trione) that is subsequently reacted to (S)-HBL by metal-free homogeneous acid/base catalysis. These reactions do not involve the C5 of glucose, leading to enantiopure (S)-HBL, produced at less than half the present cost. This approach can also be used to produce other commercially important building blocks from sustainable feedstocks: the enzymes used for trione production are active in converting xylose, leading to the acrylate co-monomer 3-hydroxypropionic acid.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102665"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144652643","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102873
Ayang Zhao , Yueyue Gao , Sihua Qi , Liangcan He
Persistent drug resistance and immune evasion driven by extracellular polymeric substances from biofilms make implant-associated biofilm infections a major clinical challenge leading to implant failure. In the November issue of Cell Biomaterials, Zhu et al. report a novel in situ nanovaccine: GaSe@PDA@activated neutrophil-membrane nanosheets (GSPN NSs). This innovation offers a neoteric solution against such infections by synergistically disrupting bacterial metabolism and inducing peripheral trained immunity.
{"title":"A nano-vaccine strategy for combatting implant-associated biofilm infections","authors":"Ayang Zhao , Yueyue Gao , Sihua Qi , Liangcan He","doi":"10.1016/j.chempr.2025.102873","DOIUrl":"10.1016/j.chempr.2025.102873","url":null,"abstract":"<div><div>Persistent drug resistance and immune evasion driven by extracellular polymeric substances from biofilms make implant-associated biofilm infections a major clinical challenge leading to implant failure. In the November issue of <em>Cell Biomaterials</em>, Zhu et al. report a novel <em>in situ</em> nanovaccine: GaSe@PDA@activated neutrophil-membrane nanosheets (GSPN NSs). This innovation offers a neoteric solution against such infections by synergistically disrupting bacterial metabolism and inducing peripheral trained immunity.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102873"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145658076","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 : 2025-12-11DOI: 10.1016/j.chempr.2025.102784
Agnieszka Bajer , Venkateswarulu Mangili , Artur R. Stefankiewicz
Self-assembled coordination architectures are emerging as powerful platforms for creating artificial enzymes that emulate the structural and functional complexity of natural biocatalysts. By combining well-defined cavities, tunable host-guest interactions, and catalytic control within confined nanoscale spaces, these systems offer unique opportunities for advancing sustainable catalysis, molecular recognition, and biomedical innovation. In this perspective, we highlight recent advances in the design and function of coordination-driven artificial enzymes, focusing on how metal-organic architectures (MOAs) can be engineered to stabilize reactive intermediates, direct substrate selectivity, and respond to external stimuli. We outline the principles behind these supramolecular systems and explore their growing potential in both industrial and therapeutic contexts.
{"title":"The rational design of coordination-driven supramolecular artificial enzymes: From catalysis to biomedicine","authors":"Agnieszka Bajer , Venkateswarulu Mangili , Artur R. Stefankiewicz","doi":"10.1016/j.chempr.2025.102784","DOIUrl":"10.1016/j.chempr.2025.102784","url":null,"abstract":"<div><div>Self-assembled coordination architectures are emerging as powerful platforms for creating artificial enzymes that emulate the structural and functional complexity of natural biocatalysts. By combining well-defined cavities, tunable host-guest interactions, and catalytic control within confined nanoscale spaces, these systems offer unique opportunities for advancing sustainable catalysis, molecular recognition, and biomedical innovation. In this perspective, we highlight recent advances in the design and function of coordination-driven artificial enzymes, focusing on how metal-organic architectures (MOAs) can be engineered to stabilize reactive intermediates, direct substrate selectivity, and respond to external stimuli. We outline the principles behind these supramolecular systems and explore their growing potential in both industrial and therapeutic contexts.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 12","pages":"Article 102784"},"PeriodicalIF":19.6,"publicationDate":"2025-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145718989","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 : 2025-12-04DOI: 10.1016/j.chempr.2025.102827
Andrea Rogolino, Stuart Linley, Papa Kwakye Kwarteng, Shannon A. Bonke, Carolina Pulignani, Erwin Reisner
Floatable photocatalysts have been demonstrated for solar fuel synthesis at the gas-liquid interface but not yet between immiscible solvents for chemical synthesis. Here, we introduce a carbon nitride and low-density plastics composite with tunable density, produced by a sustainable fabrication process for applications in liquid-liquid photocatalysis. This material enables 2D confinement, catalyst recovery, and paired, compartmentalized photocatalysis. Carbon nitride-polypropylene at the 1-butanol|water interface produced 2.7 ± 0.5 mmol L−1 h−1 aqueous H2O2 from O2 reduction and 1.5 ± 0.4 mmol L−1 h−1 butanal from butanol oxidation at room temperature (λ = 450 nm, 40 mW cm−2). Replacing 1-butanol with kraft lignin in ethyl acetate resulted in integrated H2O2 synthesis (0.78 ± 0.01 mmol L−1 h−1) and organo-soluble biomass upcycling (0.67 ± 0.01 of veratraldehyde from a model compound). Continuous processing of simultaneously produced H2O2 and valorized lignin was achieved by developing a flow reactor platform utilizing concentrated simulated solar light.
{"title":"Floatable carbon nitride-plastic composite for paired photocatalysis at the liquid-liquid interface","authors":"Andrea Rogolino, Stuart Linley, Papa Kwakye Kwarteng, Shannon A. Bonke, Carolina Pulignani, Erwin Reisner","doi":"10.1016/j.chempr.2025.102827","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102827","url":null,"abstract":"Floatable photocatalysts have been demonstrated for solar fuel synthesis at the gas-liquid interface but not yet between immiscible solvents for chemical synthesis. Here, we introduce a carbon nitride and low-density plastics composite with tunable density, produced by a sustainable fabrication process for applications in liquid-liquid photocatalysis. This material enables 2D confinement, catalyst recovery, and paired, compartmentalized photocatalysis. Carbon nitride-polypropylene at the 1-butanol|water interface produced 2.7 ± 0.5 mmol L<sup>−1</sup> h<sup>−1</sup> aqueous H<sub>2</sub>O<sub>2</sub> from O<sub>2</sub> reduction and 1.5 ± 0.4 mmol L<sup>−1</sup> h<sup>−1</sup> butanal from butanol oxidation at room temperature (λ = 450 nm, 40 mW cm<sup>−2</sup>). Replacing 1-butanol with kraft lignin in ethyl acetate resulted in integrated H<sub>2</sub>O<sub>2</sub> synthesis (0.78 ± 0.01 mmol L<sup>−1</sup> h<sup>−1</sup>) and organo-soluble biomass upcycling (0.67 ± 0.01 of veratraldehyde from a model compound). Continuous processing of simultaneously produced H<sub>2</sub>O<sub>2</sub> and valorized lignin was achieved by developing a flow reactor platform utilizing concentrated simulated solar light.","PeriodicalId":268,"journal":{"name":"Chem","volume":"34 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689093","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 : 2025-11-26DOI: 10.1016/j.chempr.2025.102830
Saber Mirzaei, Mei-Yan Gao, Ali H. Alawadhi, Ha L. Nguyen, Zihui Zhou, Vivek Singh, Daehyun D. Ahn, Davide M. Proserpio, Michael O’Keeffe, Omar M. Yaghi
The dodeca-carboxylate hexakis[3,5-bis(p-carboxyphenyl)-4,6-dimethoxyphenyl]hexabenzocoronene (HBC-LH12) molecule was synthesized, in which twelve carboxylate groups allow it to function as a twelve-connected linker. Reticulation of HBC-LH12 with yttrium(III) and uranium(VI) yielded two three-dimensional metal-organic frameworks (MOFs), termed MOF-1989 and MOF-1990, respectively. In MOF-1989, the linker, which has both hexagonal and triangular shapes with an overall hexagonal prismatic geometry, is joined by yttrium secondary building units (SBUs) of hexagonal prismatic shape to give an unprecedented edge-2-transitive (3,6,12)-c epu net. While in MOF-1990, this same linker is coordinated to triangular-shaped uranium nodes, generating triangular-triangular-hexagonal sequences and resulting in a (3,3,6)-c mzr net. The development and use of this molecule as a linker has led to new MOFs representing topologies and SBUs heretofore unobserved in reticular chemistry.
{"title":"Twelve-connected nanographene-based metal-organic frameworks","authors":"Saber Mirzaei, Mei-Yan Gao, Ali H. Alawadhi, Ha L. Nguyen, Zihui Zhou, Vivek Singh, Daehyun D. Ahn, Davide M. Proserpio, Michael O’Keeffe, Omar M. Yaghi","doi":"10.1016/j.chempr.2025.102830","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102830","url":null,"abstract":"The dodeca-carboxylate hexakis[3,5-bis(<em>p</em>-carboxyphenyl)-4,6-dimethoxyphenyl]hexabenzocoronene (HBC-LH<sub>12</sub>) molecule was synthesized, in which twelve carboxylate groups allow it to function as a twelve-connected linker. Reticulation of HBC-LH<sub>12</sub> with yttrium(III) and uranium(VI) yielded two three-dimensional metal-organic frameworks (MOFs), termed MOF-1989 and MOF-1990, respectively. In MOF-1989, the linker, which has both hexagonal and triangular shapes with an overall hexagonal prismatic geometry, is joined by yttrium secondary building units (SBUs) of hexagonal prismatic shape to give an unprecedented edge-2-transitive (3,6,12)-c <strong>epu</strong> net. While in MOF-1990, this same linker is coordinated to triangular-shaped uranium nodes, generating triangular-triangular-hexagonal sequences and resulting in a (3,3,6)-c <strong>mzr</strong> net. The development and use of this molecule as a linker has led to new MOFs representing topologies and SBUs heretofore unobserved in reticular chemistry.","PeriodicalId":268,"journal":{"name":"Chem","volume":"24 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145600132","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 : 2025-11-21DOI: 10.1016/j.chempr.2025.102822
Amreen K. Bains, Arindam Sau, Brandon S. Portela, Robert S. Paton, Garret M. Miyake, Niels H. Damrauer
Selective reduction and deuteration of heteroarenes offers a direct approach to synthesizing saturated congeners, which are vital motifs in medicinal chemistry and drug discovery. Relevant traditional synthetic methods, such as catalytic hydrogenation, primarily rely on transition-metal-mediated catalysis, elevated temperatures, and pressurized H2. Therefore, complementary metal- and H2-free methodologies that operate at room temperature and convert a wide range of heteroarenes into their saturated and, when desired, deuterium-enriched congeners are valuable. To this end, we introduce core-extended coronene-tetraesters as organic photoredox catalysts for the photoinduced reduction and deuteration of a range of heteroarenes at ambient temperature using visible light from commercially available LEDs. This protocol accommodates over nine types of heteroarenes under a common reaction condition. Mechanistic studies reveal that the reactivity is enabled by photon absorption by the in situ-generated closed-shell 2e−/H+ super-reductant.
{"title":"Reduction and deuteration of N-heteroarenes using an organic photoredox catalyst","authors":"Amreen K. Bains, Arindam Sau, Brandon S. Portela, Robert S. Paton, Garret M. Miyake, Niels H. Damrauer","doi":"10.1016/j.chempr.2025.102822","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102822","url":null,"abstract":"Selective reduction and deuteration of heteroarenes offers a direct approach to synthesizing saturated congeners, which are vital motifs in medicinal chemistry and drug discovery. Relevant traditional synthetic methods, such as catalytic hydrogenation, primarily rely on transition-metal-mediated catalysis, elevated temperatures, and pressurized H<sub>2</sub>. Therefore, complementary metal- and H<sub>2</sub>-free methodologies that operate at room temperature and convert a wide range of heteroarenes into their saturated and, when desired, deuterium-enriched congeners are valuable. To this end, we introduce core-extended coronene-tetraesters as organic photoredox catalysts for the photoinduced reduction and deuteration of a range of heteroarenes at ambient temperature using visible light from commercially available LEDs. This protocol accommodates over nine types of heteroarenes under a common reaction condition. Mechanistic studies reveal that the reactivity is enabled by photon absorption by the <em>in situ</em>-generated closed-shell 2e<sup>−</sup>/H<sup>+</sup> super-reductant.","PeriodicalId":268,"journal":{"name":"Chem","volume":"189 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145560487","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 : 2025-11-21DOI: 10.1016/j.chempr.2025.102813
Noah B. Lewis, Joseph Kelly, Joel G. Gardner, Neil K. Razdan, Shane Ardo, Thomas E. Markland, Yogesh Surendranath
Interfacial proton-coupled electron transfer (I-PCET) is typically viewed as a single elementary reaction despite general recognition that analogous solution-phase reactivity requires proton donor-acceptor pre-association. Herein, we examine the role of pre-association in I-PCET to a graphite-conjugated carboxylic acid (GC-COOH) surface by quantifying electrolyte pH and I-PCET kinetics as a function of NaClO4 concentrations up to 17 mol kg−1. In acidic and acetate-buffered media, we observed attenuations in the I-PCET rate relative to those expected given the solution pH. To account for the influence of electrolyte concentration on I-PCET rate, we propose a multiple-step model wherein the exchange of interfacial Na+ for H3O+ to form a hydrogen-bonded pre-association complex precedes rate-limiting concerted proton-electron transfer. In this model, the increased electrolyte concentration inhibits H3O+ pre-association, a phenomenon that is recovered in molecular dynamics simulations. These studies demonstrate the non-innocence of supporting electrolyte and expose the key role that pre-association equilibria play in I-PCET mechanisms.
{"title":"Ion-exchange-mediated pre-association gates interfacial PCET","authors":"Noah B. Lewis, Joseph Kelly, Joel G. Gardner, Neil K. Razdan, Shane Ardo, Thomas E. Markland, Yogesh Surendranath","doi":"10.1016/j.chempr.2025.102813","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102813","url":null,"abstract":"Interfacial proton-coupled electron transfer (I-PCET) is typically viewed as a single elementary reaction despite general recognition that analogous solution-phase reactivity requires proton donor-acceptor pre-association. Herein, we examine the role of pre-association in I-PCET to a graphite-conjugated carboxylic acid (GC-COOH) surface by quantifying electrolyte pH and I-PCET kinetics as a function of NaClO<sub>4</sub> concentrations up to 17 mol kg<sup>−1</sup>. In acidic and acetate-buffered media, we observed attenuations in the I-PCET rate relative to those expected given the solution pH. To account for the influence of electrolyte concentration on I-PCET rate, we propose a multiple-step model wherein the exchange of interfacial Na<sup>+</sup> for H<sub>3</sub>O<sup>+</sup> to form a hydrogen-bonded pre-association complex precedes rate-limiting concerted proton-electron transfer. In this model, the increased electrolyte concentration inhibits H<sub>3</sub>O<sup>+</sup> pre-association, a phenomenon that is recovered in molecular dynamics simulations. These studies demonstrate the non-innocence of supporting electrolyte and expose the key role that pre-association equilibria play in I-PCET mechanisms.","PeriodicalId":268,"journal":{"name":"Chem","volume":"65 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145560485","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 : 2025-11-20DOI: 10.1016/j.chempr.2025.102824
Xi Cao, Yan Liu, Rui Yu, Yan Yang, Ang Li, Xinyang Li, Junjie Mao
The structural regulation of copper-based catalysts is an effective strategy for realizing the electroreduction of carbon dioxide to multi-carbon (C2+) products. However, the complexity of product distribution and reaction pathways limits the achievable ampere-level current densities for C2+ products. Herein, a crystal facet engineering strategy was developed to delicately balance the protonation processes, enabling the selective formation of C2+ products at ampere-level current densities. The balance between proton activation, ∗CO formation, and C–C coupling was achieved by the in situ generation of defect sites and the control of the Cu(111)/Cu(100) ratio, overcoming current density limitations. Notably, the optimized catalyst sustained a Faradaic efficiency (FE) for C2+ products exceeding 80%, with current density increasing from 0.4 to 1.7 A cm−2 and a yield of 4.29 mmol h−1cm−2 in a flow cell. In a large-scale membrane electrode assembly, an industrial current of 15 A maintained 80% FE, achieving a yield of 39 mmol h−1.
铜基催化剂的结构调控是实现二氧化碳电还原生成多碳（C2+）产物的有效策略。然而，产物分布和反应途径的复杂性限制了C2+产物可实现的安培级电流密度。在此，开发了一种晶体面工程策略来微妙地平衡质子化过程，从而在安培级电流密度下选择性地形成C2+产物。通过原位生成缺陷位点和控制Cu(111)/Cu（100）比，克服了电流密度的限制，实现了质子活化、∗CO形成和C-C耦合之间的平衡。值得注意的是，优化后的催化剂对C2+产物的法拉第效率（FE）超过80%，电流密度从0.4增加到1.7 a cm−2，流池产率为4.29 mmol h−1cm−2。在大型膜电极组件中，15 a的工业电流维持80%的FE，获得39 mmol h−1的产率。
{"title":"Breaking ampere-level current density limitations in multi-carbon products through crystal facet engineering","authors":"Xi Cao, Yan Liu, Rui Yu, Yan Yang, Ang Li, Xinyang Li, Junjie Mao","doi":"10.1016/j.chempr.2025.102824","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102824","url":null,"abstract":"The structural regulation of copper-based catalysts is an effective strategy for realizing the electroreduction of carbon dioxide to multi-carbon (C<sub>2+</sub>) products. However, the complexity of product distribution and reaction pathways limits the achievable ampere-level current densities for C<sub>2+</sub> products. Herein, a crystal facet engineering strategy was developed to delicately balance the protonation processes, enabling the selective formation of C<sub>2+</sub> products at ampere-level current densities. The balance between proton activation, ∗CO formation, and C–C coupling was achieved by the <em>in situ</em> generation of defect sites and the control of the Cu(111)/Cu(100) ratio, overcoming current density limitations. Notably, the optimized catalyst sustained a Faradaic efficiency (FE) for C<sub>2+</sub> products exceeding 80%, with current density increasing from 0.4 to 1.7 A cm<sup>−2</sup> and a yield of 4.29 mmol h<sup>−1</sup>cm<sup>−2</sup> in a flow cell. In a large-scale membrane electrode assembly, an industrial current of 15 A maintained 80% FE, achieving a yield of 39 mmol h<sup>−1</sup>.","PeriodicalId":268,"journal":{"name":"Chem","volume":"79 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145554871","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}
The bidirectional photocurrent holds great research significance in numerous photoelectrochemical (PEC) applications, owing to its superior accuracy and multifunctionality. Herein, we introduce an innovative concept of reverse photocurrent (|Ilight| < |Idark|), where the photocurrent direction switches within the cathode due to differing oxygen reduction activities at dual sites. When platinum nanoparticles are incorporated with carbon nitride nanosheets, a facile conversion of the traditional photocurrent (|Ilight| > |Idark|) into a reverse photocurrent with an enhancement of 22 times is achieved. Compared with traditional photocurrent characteristics, this reverse photocurrent not only reveals a new mechanism for PEC light/dark reactions but also serves as a new strategy to induce the changeover of photocurrent direction. Leveraging this bidirectional-photocurrent approach, more sensitive evaluation of aptamer-target interactions and target detection has been successfully realized. This study will offer fresh insights into photoelectrode design in the PEC analysis and surface reaction monitoring.
{"title":"Oxygen reduction active site regulation enabled reverse photocurrent in photoelectrochemical sensing","authors":"Ying Qin, Yuanxing Chen, Wenhong Yang, Rong Tan, Jingyi Zhang, Runshi Xiao, Mingwang Liu, Liuyong Hu, Wenling Gu, Chengzhou Zhu","doi":"10.1016/j.chempr.2025.102821","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102821","url":null,"abstract":"The bidirectional photocurrent holds great research significance in numerous photoelectrochemical (PEC) applications, owing to its superior accuracy and multifunctionality. Herein, we introduce an innovative concept of reverse photocurrent (|I<sub>light</sub>| < |I<sub>dark</sub>|), where the photocurrent direction switches within the cathode due to differing oxygen reduction activities at dual sites. When platinum nanoparticles are incorporated with carbon nitride nanosheets, a facile conversion of the traditional photocurrent (|I<sub>light</sub>| > |I<sub>dark</sub>|) into a reverse photocurrent with an enhancement of 22 times is achieved. Compared with traditional photocurrent characteristics, this reverse photocurrent not only reveals a new mechanism for PEC light/dark reactions but also serves as a new strategy to induce the changeover of photocurrent direction. Leveraging this bidirectional-photocurrent approach, more sensitive evaluation of aptamer-target interactions and target detection has been successfully realized. This study will offer fresh insights into photoelectrode design in the PEC analysis and surface reaction monitoring.","PeriodicalId":268,"journal":{"name":"Chem","volume":"30 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-11-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145554870","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}
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