Pub Date : 2026-01-05DOI: 10.1038/s41557-025-02024-2
Yifei Xu, Bingjun Xu
While heterogeneous hydrogenation processes are widely employed industrial reactions, there is a murky understanding of how heterolytic hydrogenations operate. Now, interfacial polarization is shown to have a profound impact over catalysis by platinum surfaces, demonstrating the hidden role of electrochemistry in thermal catalysis.
{"title":"Electrochemistry lurks beneath the surface of thermocatalytic hydrogenations","authors":"Yifei Xu, Bingjun Xu","doi":"10.1038/s41557-025-02024-2","DOIUrl":"10.1038/s41557-025-02024-2","url":null,"abstract":"While heterogeneous hydrogenation processes are widely employed industrial reactions, there is a murky understanding of how heterolytic hydrogenations operate. Now, interfacial polarization is shown to have a profound impact over catalysis by platinum surfaces, demonstrating the hidden role of electrochemistry in thermal catalysis.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 1","pages":"10-11"},"PeriodicalIF":20.2,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145905278","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 : 2026-01-02DOI: 10.1038/s41557-025-02032-2
Lisa Kennedy, Dominic J. Campopiano
Catalysis has been a standard topic taught in university chemistry courses over the past century yet biocatalysis — or enzyme catalysis — has only recently been integrated into standard chemistry curriculum despite its broad applicability in industry. In a fourth year undergraduate research project course, students can now choose to explore interesting chemical transformations in the lab using biocatalysis instead of traditional synthetic chemistry approaches.
{"title":"Bringing biocatalysis into teaching labs","authors":"Lisa Kennedy, Dominic J. Campopiano","doi":"10.1038/s41557-025-02032-2","DOIUrl":"10.1038/s41557-025-02032-2","url":null,"abstract":"Catalysis has been a standard topic taught in university chemistry courses over the past century yet biocatalysis — or enzyme catalysis — has only recently been integrated into standard chemistry curriculum despite its broad applicability in industry. In a fourth year undergraduate research project course, students can now choose to explore interesting chemical transformations in the lab using biocatalysis instead of traditional synthetic chemistry approaches.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 1","pages":"1-3"},"PeriodicalIF":20.2,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145905274","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 : 2026-01-02DOI: 10.1038/s41557-025-02030-4
Tian Chen, Wenjun Tang
Chiral phosphorus(V) compounds are vital in the fields of catalysis, pharmaceuticals and nucleic acids, yet their stereoselective synthesis has been difficult to achieve. Now, a bio-inspired catalyst has brought excellent stereocontrol to the classic Atherton–Todd reaction, providing a simple route to a diverse set of chiral phosphorus(V) building blocks.
{"title":"Biomimetic catalysis enables asymmetric Atherton–Todd reaction","authors":"Tian Chen, Wenjun Tang","doi":"10.1038/s41557-025-02030-4","DOIUrl":"10.1038/s41557-025-02030-4","url":null,"abstract":"Chiral phosphorus(V) compounds are vital in the fields of catalysis, pharmaceuticals and nucleic acids, yet their stereoselective synthesis has been difficult to achieve. Now, a bio-inspired catalyst has brought excellent stereocontrol to the classic Atherton–Todd reaction, providing a simple route to a diverse set of chiral phosphorus(V) building blocks.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 1","pages":"6-7"},"PeriodicalIF":20.2,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145905279","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 : 2026-01-02DOI: 10.1038/s41557-025-02025-1
Fan Wang, Jian-Ping Tan, Ganlu Qian, Siqiang Fang, Zanjiao Liu, Kehan Li, Jiayan Zheng, Jia-Hong Wu, Xin Hong, Tianli Wang
The Atherton–Todd (A–T) reaction has long been regarded as a cornerstone method for synthesizing a wide array of phosphorus(V) compounds. However, despite its vast synthetic potential, achieving precise stereocontrol in this transformation remains a challenge. Here we present the highly efficient and direct asymmetric A–T reaction, using biomimetic peptide–phosphonium salt catalysts to enable the stepwise and precise synthesis of a diverse array of phosphorus(V)-based scaffolds. We demonstrate the efficient generation of three distinct stereogenic phosphorus(V) species—phosphoryl chlorides, phosphinates and phosphonates—while maintaining exceptional functional group compatibility and delivering outstanding enantioselectivity. Our mechanistic studies, complemented by density functional theory calculations, uncover the ability of the peptide–phosphonium salt catalysts to modulate the chiral environment, selectively recognizing and pre-assembling phosphorus substrates and/or nucleophilic species. This finely tuned chiral cavity facilitates a stepwise-controllable, enantioselective A–T reaction, providing an elegant strategy for the synthesis of stereochemically defined phosphorus ligands, bioactive molecules and oligonucleotides. In complex reaction systems featuring intricate product and pathway possibilities, achieving simultaneous control over multiple selectivities remains highly challenging. Now it has been demonstrated that biomimetic peptide–phosphonium salts can concurrently impart stepwise and stereochemical control in the asymmetric Atherton–Todd reaction, which enables efficient access to diverse P-stereogenic platform molecules.
{"title":"Stepwise-controllable catalytic asymmetric Atherton–Todd reaction to access diverse P(V)-stereogenic compounds","authors":"Fan Wang, Jian-Ping Tan, Ganlu Qian, Siqiang Fang, Zanjiao Liu, Kehan Li, Jiayan Zheng, Jia-Hong Wu, Xin Hong, Tianli Wang","doi":"10.1038/s41557-025-02025-1","DOIUrl":"10.1038/s41557-025-02025-1","url":null,"abstract":"The Atherton–Todd (A–T) reaction has long been regarded as a cornerstone method for synthesizing a wide array of phosphorus(V) compounds. However, despite its vast synthetic potential, achieving precise stereocontrol in this transformation remains a challenge. Here we present the highly efficient and direct asymmetric A–T reaction, using biomimetic peptide–phosphonium salt catalysts to enable the stepwise and precise synthesis of a diverse array of phosphorus(V)-based scaffolds. We demonstrate the efficient generation of three distinct stereogenic phosphorus(V) species—phosphoryl chlorides, phosphinates and phosphonates—while maintaining exceptional functional group compatibility and delivering outstanding enantioselectivity. Our mechanistic studies, complemented by density functional theory calculations, uncover the ability of the peptide–phosphonium salt catalysts to modulate the chiral environment, selectively recognizing and pre-assembling phosphorus substrates and/or nucleophilic species. This finely tuned chiral cavity facilitates a stepwise-controllable, enantioselective A–T reaction, providing an elegant strategy for the synthesis of stereochemically defined phosphorus ligands, bioactive molecules and oligonucleotides. In complex reaction systems featuring intricate product and pathway possibilities, achieving simultaneous control over multiple selectivities remains highly challenging. Now it has been demonstrated that biomimetic peptide–phosphonium salts can concurrently impart stepwise and stereochemical control in the asymmetric Atherton–Todd reaction, which enables efficient access to diverse P-stereogenic platform molecules.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 1","pages":"23-32"},"PeriodicalIF":20.2,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145905276","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 : 2026-01-02DOI: 10.1038/s41557-025-02027-z
Control of the surface chemistry of Au nanoparticles is central to their functionality, yet probing the interfacial chemistry under operando conditions is challenging. Now, precision nanoparticle gaps provide a spectroscopic window to observe the chemical changes at Au interfaces during electrochemical cycling, revealing the formation of an Au–Cl adlayer that modulates the surface chemistry.
{"title":"Protecting skins of Au–Cl can stabilize Au nanostructures","authors":"","doi":"10.1038/s41557-025-02027-z","DOIUrl":"10.1038/s41557-025-02027-z","url":null,"abstract":"Control of the surface chemistry of Au nanoparticles is central to their functionality, yet probing the interfacial chemistry under operando conditions is challenging. Now, precision nanoparticle gaps provide a spectroscopic window to observe the chemical changes at Au interfaces during electrochemical cycling, revealing the formation of an Au–Cl adlayer that modulates the surface chemistry.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 2","pages":"225-226"},"PeriodicalIF":20.2,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145892617","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 : 2026-01-02DOI: 10.1038/s41557-025-02012-6
Yuena Wang, Tao Hu, Lin Zhu, Shaoshuai Xie, Xi Yang, Caifeng Xu, Yansheng Zhai, Youming Li, Xiaoyan Huang, Bo Yang, Gang Li
Despite the crucial biological functions of arginine, its reactivity and ligandability within the human proteome remain largely unexplored. Here we apply activity-based protein profiling (ABPP) with phenylglyoxal-based chemical probes to map arginine reactivity globally. Screening phenylglyoxal derivatives identified a probe with enhanced coverage and selectivity, enabling quantification of 4,606 arginine sites across human cell lines. Among these, critical residues regulate liquid–liquid phase separation. Arginine reactivity was further assessed by on-beads reductive dimethylation proteomics, revealing a subset of hyper-reactive sites. Competitive fragment screening using data-independent acquisition ABPP (DIA-ABPP) generated a ligandability map of arginine residues across 60 dicarbonyl compounds. This dataset revealed ligandable arginines that modulate protein activity, in particular protein–protein interactions, highlighting potential covalent drug targets. Together, this work provides a proteome-wide profile of arginine reactivity and ligandability, offering insights into the functional landscape of arginines and expanding the scope of covalent drug discovery to include arginine-targeting molecules. The reactivity and ligandability of arginine within the human proteome have been largely unexplored despite it being involved in various biological functions. Now, arginine reactivity and ligandability have been mapped across the proteome, revealing hyper-reactive sites and identifying residues that control liquid–liquid phase separation, protein activity and protein–protein interactions.
{"title":"Global profiling of arginine reactivity and ligandability in the human proteome","authors":"Yuena Wang, Tao Hu, Lin Zhu, Shaoshuai Xie, Xi Yang, Caifeng Xu, Yansheng Zhai, Youming Li, Xiaoyan Huang, Bo Yang, Gang Li","doi":"10.1038/s41557-025-02012-6","DOIUrl":"10.1038/s41557-025-02012-6","url":null,"abstract":"Despite the crucial biological functions of arginine, its reactivity and ligandability within the human proteome remain largely unexplored. Here we apply activity-based protein profiling (ABPP) with phenylglyoxal-based chemical probes to map arginine reactivity globally. Screening phenylglyoxal derivatives identified a probe with enhanced coverage and selectivity, enabling quantification of 4,606 arginine sites across human cell lines. Among these, critical residues regulate liquid–liquid phase separation. Arginine reactivity was further assessed by on-beads reductive dimethylation proteomics, revealing a subset of hyper-reactive sites. Competitive fragment screening using data-independent acquisition ABPP (DIA-ABPP) generated a ligandability map of arginine residues across 60 dicarbonyl compounds. This dataset revealed ligandable arginines that modulate protein activity, in particular protein–protein interactions, highlighting potential covalent drug targets. Together, this work provides a proteome-wide profile of arginine reactivity and ligandability, offering insights into the functional landscape of arginines and expanding the scope of covalent drug discovery to include arginine-targeting molecules. The reactivity and ligandability of arginine within the human proteome have been largely unexplored despite it being involved in various biological functions. Now, arginine reactivity and ligandability have been mapped across the proteome, revealing hyper-reactive sites and identifying residues that control liquid–liquid phase separation, protein activity and protein–protein interactions.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 2","pages":"374-385"},"PeriodicalIF":20.2,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145892653","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 : 2025-12-19DOI: 10.1038/s41557-025-02009-1
Xiyue Zhang, Panxing Bai, Travis P. Pollard, Xiaoming Ren, Zheng Li, Minsung Baek, Guorui Cai, Caitlin D. Parke, Yijie Liu, Wenhao Xu, Yue Li, Xilin Chen, Paul Albertus, Oleg Borodin, Chunsheng Wang
The remarkable success of Li-ion batteries originates from the formation of solid electrolyte interphases through electrolyte reduction on anodes. Transferring electrolyte reduction to the cathode could generate cathode–electrolyte interphases that could further improve battery performances, but the implementation has been challenging. Here we introduce a bimolecular nucleophilic substitution reaction-assisted electrolyte reduction strategy that elevates the reduction potential of electrolytes and enables the formation of either passivating or non-passivating LiF-rich cathode–electrolyte interphases. Spectroscopic studies revealed that the passivation behaviour of these interphases is governed by the diffusivity of sulfite-based solvent reduction products and the fluoroborate anion type involved in the reaction. Guided by this principle, we have developed electrolytes that can either enhance the energy and power of primary batteries or extend the cycle life in rechargeable batteries. We also extend this electrolyte design principle from fluoroborate anions to SiCl4. Collectively, this work establishes a universal approach for electrolyte and interphase design that spans organic chemistry, interfacial chemistry and electrochemistry. The success of Li batteries relies on electrolyte reduction at anodes for interphase formation, yet controlled interphase formation on high-energy cathodes has proven challenging. Now it has been shown that a bimolecular nucleophilic substitution-assisted strategy advances both primary and secondary batteries by regulating the electrolyte reduction potential and interphase passivation capability.
{"title":"Electrolyte reduction on cathodes to enhance the performance of high-energy batteries","authors":"Xiyue Zhang, Panxing Bai, Travis P. Pollard, Xiaoming Ren, Zheng Li, Minsung Baek, Guorui Cai, Caitlin D. Parke, Yijie Liu, Wenhao Xu, Yue Li, Xilin Chen, Paul Albertus, Oleg Borodin, Chunsheng Wang","doi":"10.1038/s41557-025-02009-1","DOIUrl":"10.1038/s41557-025-02009-1","url":null,"abstract":"The remarkable success of Li-ion batteries originates from the formation of solid electrolyte interphases through electrolyte reduction on anodes. Transferring electrolyte reduction to the cathode could generate cathode–electrolyte interphases that could further improve battery performances, but the implementation has been challenging. Here we introduce a bimolecular nucleophilic substitution reaction-assisted electrolyte reduction strategy that elevates the reduction potential of electrolytes and enables the formation of either passivating or non-passivating LiF-rich cathode–electrolyte interphases. Spectroscopic studies revealed that the passivation behaviour of these interphases is governed by the diffusivity of sulfite-based solvent reduction products and the fluoroborate anion type involved in the reaction. Guided by this principle, we have developed electrolytes that can either enhance the energy and power of primary batteries or extend the cycle life in rechargeable batteries. We also extend this electrolyte design principle from fluoroborate anions to SiCl4. Collectively, this work establishes a universal approach for electrolyte and interphase design that spans organic chemistry, interfacial chemistry and electrochemistry. The success of Li batteries relies on electrolyte reduction at anodes for interphase formation, yet controlled interphase formation on high-energy cathodes has proven challenging. Now it has been shown that a bimolecular nucleophilic substitution-assisted strategy advances both primary and secondary batteries by regulating the electrolyte reduction potential and interphase passivation capability.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 2","pages":"418-427"},"PeriodicalIF":20.2,"publicationDate":"2025-12-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145794229","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 : 2025-12-10DOI: 10.1038/s41557-025-02013-5
Spatiotemporal control of polymerization is typically achieved with switchable catalysts. In an alternative approach, latency is now built into the monomer. A photoswitchable quadricyclane–norbornadiene pair, activated by heat or photothermal conversion, keeps initiator-premixed metathesis feeds stable yet reactive on demand, enabling reproducible polymerization with spatial precision.
{"title":"Photoswitchable latent monomers enable on‑demand metathesis","authors":"","doi":"10.1038/s41557-025-02013-5","DOIUrl":"10.1038/s41557-025-02013-5","url":null,"abstract":"Spatiotemporal control of polymerization is typically achieved with switchable catalysts. In an alternative approach, latency is now built into the monomer. A photoswitchable quadricyclane–norbornadiene pair, activated by heat or photothermal conversion, keeps initiator-premixed metathesis feeds stable yet reactive on demand, enabling reproducible polymerization with spatial precision.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 1","pages":"12-13"},"PeriodicalIF":20.2,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145724806","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 : 2025-12-08DOI: 10.1038/s41557-025-02011-7
Nir Lemcoff, Ronny Niv, Keren Iudanov, Gil Gordon, Aritra Biswas, Uri Ben-Nun, Ofir Shelonchik, N. Gabriel Lemcoff, Yossi Weizmann
Our understanding of polymers has given rise to fundamental changes in society. Nonetheless, there is much room to further develop and improve creative techniques to enable advanced materials. At the frontiers of this endeavour is the development of switchable catalysts aimed at providing spatiotemporal control over polymerization reactions. Here we present an alternative to the conventional catalyst-centred approach by using quadricyclane–norbornadiene isomerization as a switchable monomer for ring-opening metathesis polymerization. The on-demand polymerization of four norbornadiene derivatives was achieved using two different ruthenium-based olefin metathesis initiators. The latent quadricyclane isomer generated remarkably stable formulations upon mixing with ruthenium initiators, remaining unchanged for up to 7 weeks. In addition to conventional heating, the latent monomer could also be activated by the photothermal response of gold bipyramids, leading to highly efficient polymerization reactions amenable to 3D printing techniques. Finally, a one-pot diblock copolymerization strategy and sequential curing process inaccessible by traditional methodologies was developed, exploiting the exceptional latency of the monomers. Latent catalysis in olefin metathesis has seen great progress over the years, leading to key advances in the properties of polymers and 3D printing technologies. Now it is shown that the latency mechanism can be extended to the monomer through quadricyclane–norbornadiene interconversion, expanding the tools available to this field.
{"title":"Photoswitchable olefins as latent metathesis monomers for controlled polymerization","authors":"Nir Lemcoff, Ronny Niv, Keren Iudanov, Gil Gordon, Aritra Biswas, Uri Ben-Nun, Ofir Shelonchik, N. Gabriel Lemcoff, Yossi Weizmann","doi":"10.1038/s41557-025-02011-7","DOIUrl":"10.1038/s41557-025-02011-7","url":null,"abstract":"Our understanding of polymers has given rise to fundamental changes in society. Nonetheless, there is much room to further develop and improve creative techniques to enable advanced materials. At the frontiers of this endeavour is the development of switchable catalysts aimed at providing spatiotemporal control over polymerization reactions. Here we present an alternative to the conventional catalyst-centred approach by using quadricyclane–norbornadiene isomerization as a switchable monomer for ring-opening metathesis polymerization. The on-demand polymerization of four norbornadiene derivatives was achieved using two different ruthenium-based olefin metathesis initiators. The latent quadricyclane isomer generated remarkably stable formulations upon mixing with ruthenium initiators, remaining unchanged for up to 7 weeks. In addition to conventional heating, the latent monomer could also be activated by the photothermal response of gold bipyramids, leading to highly efficient polymerization reactions amenable to 3D printing techniques. Finally, a one-pot diblock copolymerization strategy and sequential curing process inaccessible by traditional methodologies was developed, exploiting the exceptional latency of the monomers. Latent catalysis in olefin metathesis has seen great progress over the years, leading to key advances in the properties of polymers and 3D printing technologies. Now it is shown that the latency mechanism can be extended to the monomer through quadricyclane–norbornadiene interconversion, expanding the tools available to this field.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"18 1","pages":"51-60"},"PeriodicalIF":20.2,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704692","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}
Impurity ions pose a major challenge towards diversifying water sources for electrolysis. In particular, chloride impurities in low-grade water diminish the selectivity and longevity of water electrolysers. Here we demonstrate that alkali cations can regulate chloride diffusion, allowing a marked improvement in the reaction selectivity of water oxidation. Rotating ring-disk electrode measurements exhibit anomalous positive intercepts in the Levich plot, indicating a diffusional barrier that is cation dependent yet independent of rotational speed. To rationalize this barrier, we propose a simple modification to the Levich model, in which the cation-dependent diffusion coefficient is at least two orders of magnitude lower than that of the bulk solution. The potential of maximum entropy and the structural entropy of hydration both indicate that the diffusion barrier increases when the first hydration shell is structurally rigid (Li+ > Na+ > H+ > K+ > Cs+). Our findings offer a strategy to suppress impurity-driven side reactions at the high current densities relevant to water electrolysis.
{"title":"Hydration entropy of cations regulates chloride ion diffusion during electrochemical chlorine evolution.","authors":"Taejung Lim,Hideshi Ooka,Yuhang Yu,Takeharu Murakami,Satoshi Wada,Ryuhei Nakamura","doi":"10.1038/s41557-025-02014-4","DOIUrl":"https://doi.org/10.1038/s41557-025-02014-4","url":null,"abstract":"Impurity ions pose a major challenge towards diversifying water sources for electrolysis. In particular, chloride impurities in low-grade water diminish the selectivity and longevity of water electrolysers. Here we demonstrate that alkali cations can regulate chloride diffusion, allowing a marked improvement in the reaction selectivity of water oxidation. Rotating ring-disk electrode measurements exhibit anomalous positive intercepts in the Levich plot, indicating a diffusional barrier that is cation dependent yet independent of rotational speed. To rationalize this barrier, we propose a simple modification to the Levich model, in which the cation-dependent diffusion coefficient is at least two orders of magnitude lower than that of the bulk solution. The potential of maximum entropy and the structural entropy of hydration both indicate that the diffusion barrier increases when the first hydration shell is structurally rigid (Li+ > Na+ > H+ > K+ > Cs+). Our findings offer a strategy to suppress impurity-driven side reactions at the high current densities relevant to water electrolysis.","PeriodicalId":18909,"journal":{"name":"Nature chemistry","volume":"35 1","pages":""},"PeriodicalIF":21.8,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145704694","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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