Pub Date : 2026-10-08Epub Date: 2026-04-15DOI: 10.1016/j.chempr.2026.103025
Wen Wang (王文), Xinyuan Zhao (赵心远), Qi Li (李琪), Yue Zhang (张月), Qifan Wang (王启帆), Yao Xie (谢瑶), Fangyu Ren (任方煜), Shengli Hou (侯胜利), Bin Zhao (赵斌)
<div><ul><li><span>•</span><span><div>CuIn-CPT sets a record turnover number for asymmetric carbonate synthesis from CO<sub>2</sub></div></span></li><li><span>•</span><span><div>Synergistic catalysis ensures high efficiency and stability in multicomponent reactions</div></span></li><li><span>•</span><span><div>Bimetallic [Cu<sub>4</sub>] and [In<sub>3</sub>] clusters in MOFs drive tandem catalysis for CO<sub>2</sub> conversion</div></span></li></ul></div><div>Transforming CO<sub>2</sub> into valuable asymmetric carbonates is crucial for green chemistry but remains challenging. This work presents a copper-indium framework that achieves record efficiency in synthesizing these compounds from CO<sub>2</sub> and alcohols under mild, solvent-free conditions. It maintains high stability, and the turnover number is much higher than that of reported noble metal catalysts. As the first metal-organic framework (MOF) catalyst for this reaction, it demonstrates the potential of non-precious metal systems in carbon utilization technologies.</div><div><div>The synthesis of asymmetric carbonates from renewable CO<sub>2</sub> is important for sustainable chemistry but often suffers from low efficiency, harsh reaction conditions, and noble metal catalysts. Achieving this efficient transformation under mild conditions by non-noble metal catalysts remains a great challenge. Herein, a framework {[In<sub>3</sub>(<em>μ</em><sub>3</sub>-O)(H<sub>2</sub>O)Cu<sub>4</sub>(CPT)<sub>4</sub>I<sub>2</sub>]⋅(NO<sub>3</sub>)⋅1.5H<sub>2</sub>O⋅3DMF}<sub>n</sub> (CuIn-CPT, CPT = 3,5-bis(4′-carboxyphenyl)-1,2,4-triazole) was synthesized, assembled from a [Cu<sub>12</sub>In<sub>18</sub>] nanocage with multiple Cu<sup>I</sup> and In<sup>III</sup> Lewis acid sites, and it exhibits good thermal and chemical stabilities. It achieves up to 98% yield in multicomponent reactions of CO<sub>2</sub>, propargyl alcohols, and primary alcohols without solvent under mild conditions, with a record turnover number of 4,844—ten times higher than top Ag-based catalysts—and excellent recyclability over 10 cycles. Density functional theory (DFT) calculations and mechanistic studies confirm that the synergistic effect between [Cu<sub>4</sub>] and [In<sub>3</sub>] clusters enhances catalytic efficiency. This work provides an inspiration for developing efficient non-noble metal heterogeneous catalysts in CO<sub>2</sub> conversion.</div></div><div>The synthesis of asymmetric carbonates from renewable CO<sub>2</sub> is important for sustainable chemistry but often suffers from low efficiency, harsh reaction conditions, and noble metal catalysts. Achieving this efficient transformation under mild conditions by non-noble metal catalysts remains a great challenge. Herein, a framework {[In<sub>3</sub>(<em>μ</em><sub>3</sub>-O)(H<sub>2</sub>O)Cu<sub>4</sub>(CPT)<sub>4</sub>I<sub>2</sub>]⋅(NO<sub>3</sub>)⋅1.5H<sub>2</sub>O⋅3DMF}<sub>n</sub> (CuIn-CPT, CPT = 3,5-bis(4′-carboxyphenyl)-1,2,4-triazole) was synthesize
{"title":"Bimetallic synergistic catalysis in MOFs toward transforming CO2 into carbonates with a record turnover number","authors":"Wen Wang (王文), Xinyuan Zhao (赵心远), Qi Li (李琪), Yue Zhang (张月), Qifan Wang (王启帆), Yao Xie (谢瑶), Fangyu Ren (任方煜), Shengli Hou (侯胜利), Bin Zhao (赵斌)","doi":"10.1016/j.chempr.2026.103025","DOIUrl":"10.1016/j.chempr.2026.103025","url":null,"abstract":"<div><ul><li><span>•</span><span><div>CuIn-CPT sets a record turnover number for asymmetric carbonate synthesis from CO<sub>2</sub></div></span></li><li><span>•</span><span><div>Synergistic catalysis ensures high efficiency and stability in multicomponent reactions</div></span></li><li><span>•</span><span><div>Bimetallic [Cu<sub>4</sub>] and [In<sub>3</sub>] clusters in MOFs drive tandem catalysis for CO<sub>2</sub> conversion</div></span></li></ul></div><div>Transforming CO<sub>2</sub> into valuable asymmetric carbonates is crucial for green chemistry but remains challenging. This work presents a copper-indium framework that achieves record efficiency in synthesizing these compounds from CO<sub>2</sub> and alcohols under mild, solvent-free conditions. It maintains high stability, and the turnover number is much higher than that of reported noble metal catalysts. As the first metal-organic framework (MOF) catalyst for this reaction, it demonstrates the potential of non-precious metal systems in carbon utilization technologies.</div><div><div>The synthesis of asymmetric carbonates from renewable CO<sub>2</sub> is important for sustainable chemistry but often suffers from low efficiency, harsh reaction conditions, and noble metal catalysts. Achieving this efficient transformation under mild conditions by non-noble metal catalysts remains a great challenge. Herein, a framework {[In<sub>3</sub>(<em>μ</em><sub>3</sub>-O)(H<sub>2</sub>O)Cu<sub>4</sub>(CPT)<sub>4</sub>I<sub>2</sub>]⋅(NO<sub>3</sub>)⋅1.5H<sub>2</sub>O⋅3DMF}<sub>n</sub> (CuIn-CPT, CPT = 3,5-bis(4′-carboxyphenyl)-1,2,4-triazole) was synthesized, assembled from a [Cu<sub>12</sub>In<sub>18</sub>] nanocage with multiple Cu<sup>I</sup> and In<sup>III</sup> Lewis acid sites, and it exhibits good thermal and chemical stabilities. It achieves up to 98% yield in multicomponent reactions of CO<sub>2</sub>, propargyl alcohols, and primary alcohols without solvent under mild conditions, with a record turnover number of 4,844—ten times higher than top Ag-based catalysts—and excellent recyclability over 10 cycles. Density functional theory (DFT) calculations and mechanistic studies confirm that the synergistic effect between [Cu<sub>4</sub>] and [In<sub>3</sub>] clusters enhances catalytic efficiency. This work provides an inspiration for developing efficient non-noble metal heterogeneous catalysts in CO<sub>2</sub> conversion.</div></div><div>The synthesis of asymmetric carbonates from renewable CO<sub>2</sub> is important for sustainable chemistry but often suffers from low efficiency, harsh reaction conditions, and noble metal catalysts. Achieving this efficient transformation under mild conditions by non-noble metal catalysts remains a great challenge. Herein, a framework {[In<sub>3</sub>(<em>μ</em><sub>3</sub>-O)(H<sub>2</sub>O)Cu<sub>4</sub>(CPT)<sub>4</sub>I<sub>2</sub>]⋅(NO<sub>3</sub>)⋅1.5H<sub>2</sub>O⋅3DMF}<sub>n</sub> (CuIn-CPT, CPT = 3,5-bis(4′-carboxyphenyl)-1,2,4-triazole) was synthesize","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 103025"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147709289","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 : 2026-10-08Epub Date: 2026-03-26DOI: 10.1016/j.chempr.2026.102993
Ofek Vardi, Nir Yuran, Ella Manuela Jakob, Gili Ben-Nissan, Shira Yochelis, Michal Sharon, Yossi Paltiel
<div><ul><li><span>•</span><span><div>Spin-polarized magnetic filters induce carbon isotope fractionation in L-methionine</div></span></li><li><span>•</span><span><div>Volume-resolved elution reveals metastable spin-dependent interactions</div></span></li><li><span>•</span><span><div>Chirality couples electronic spin selectivity to isotope chemistry</div></span></li><li><span>•</span><span><div>Spin-dependent effects may shape isotopic signatures in early biomolecules</div></span></li></ul></div><div>Isotopic fractionation in biomolecules provides key insight into chemical and biochemical formation pathways, yet the mechanisms underlying isotope selectivity in chiral molecular systems remain poorly understood. This work demonstrates a direct experimental connection between spin-dependent interactions and isotopic effects in a chiral amino acid, showing that molecules differing only in their carbon isotope composition interact differently with oppositely magnetized surfaces. These findings reveal a previously unexplored contribution of electronic spin polarization to isotopic behavior in molecular systems.</div><div>More broadly, the results introduce spin selectivity as a new physical dimension in isotope chemistry. In the longer term, such spin- and chirality-dependent interactions may enable new approaches for isotope discrimination or separation in chiral chemical environments, with potential relevance to analytical chemistry and materials design. By linking magnetic interactions, molecular chirality, and isotope effects, this study establishes a framework for investigating how subtle spin-mediated processes can influence isotopic outcomes in complex molecular systems.</div><div><div>Distinct isotopic fractionation in biomolecules, compared with atmospheric values, reflects their biosynthetic origin. Monitoring these fractionation changes offers a valuable approach for probing early metabolic networks. A key question in the study of life’s origins is the role of electronic spin and magnetic surfaces in symmetry breaking and the emergence of homochirality. Here, we used magnetic filters to show that the dynamical interaction with the magnetic surfaces changes the isotope fractions of <sup>13</sup>C L-methionine compared with <sup>12</sup>C L-methionine. Specifically, mass spectrometry analysis reveals that the isotopic fractionation of both natural and ¹³C-enriched L-methionine is influenced by electron spin-dependent interactions.</div></div><div>Distinct isotopic fractionation in biomolecules, compared with atmospheric values, reflects their biosynthetic origin. Monitoring these fractionation changes offers a valuable approach for probing early metabolic networks. A key question in the study of life’s origins is the role of electronic spin and magnetic surfaces in symmetry breaking and the emergence of homochirality. Here, we used magnetic filters to show that the dynamical interaction with the magnetic surfaces changes the isotope fractions
与大气值相比，生物分子中不同的同位素分馏反映了它们的生物合成来源。监测这些分馏变化为探测早期代谢网络提供了一种有价值的方法。研究生命起源的一个关键问题是电子自旋和磁性表面在对称破缺和同手性出现中的作用。在这里，我们使用磁性过滤器来证明与磁性表面的动态相互作用改变了13C l -蛋氨酸与12C l -蛋氨酸的同位素分数。具体来说，质谱分析表明，天然和¹³c富集的l -蛋氨酸的同位素分馏都受到电子自旋依赖相互作用的影响。
{"title":"Spin-dependent isotopic fractionation of L-methionine","authors":"Ofek Vardi, Nir Yuran, Ella Manuela Jakob, Gili Ben-Nissan, Shira Yochelis, Michal Sharon, Yossi Paltiel","doi":"10.1016/j.chempr.2026.102993","DOIUrl":"10.1016/j.chempr.2026.102993","url":null,"abstract":"<div><ul><li><span>•</span><span><div>Spin-polarized magnetic filters induce carbon isotope fractionation in L-methionine</div></span></li><li><span>•</span><span><div>Volume-resolved elution reveals metastable spin-dependent interactions</div></span></li><li><span>•</span><span><div>Chirality couples electronic spin selectivity to isotope chemistry</div></span></li><li><span>•</span><span><div>Spin-dependent effects may shape isotopic signatures in early biomolecules</div></span></li></ul></div><div>Isotopic fractionation in biomolecules provides key insight into chemical and biochemical formation pathways, yet the mechanisms underlying isotope selectivity in chiral molecular systems remain poorly understood. This work demonstrates a direct experimental connection between spin-dependent interactions and isotopic effects in a chiral amino acid, showing that molecules differing only in their carbon isotope composition interact differently with oppositely magnetized surfaces. These findings reveal a previously unexplored contribution of electronic spin polarization to isotopic behavior in molecular systems.</div><div>More broadly, the results introduce spin selectivity as a new physical dimension in isotope chemistry. In the longer term, such spin- and chirality-dependent interactions may enable new approaches for isotope discrimination or separation in chiral chemical environments, with potential relevance to analytical chemistry and materials design. By linking magnetic interactions, molecular chirality, and isotope effects, this study establishes a framework for investigating how subtle spin-mediated processes can influence isotopic outcomes in complex molecular systems.</div><div><div>Distinct isotopic fractionation in biomolecules, compared with atmospheric values, reflects their biosynthetic origin. Monitoring these fractionation changes offers a valuable approach for probing early metabolic networks. A key question in the study of life’s origins is the role of electronic spin and magnetic surfaces in symmetry breaking and the emergence of homochirality. Here, we used magnetic filters to show that the dynamical interaction with the magnetic surfaces changes the isotope fractions of <sup>13</sup>C L-methionine compared with <sup>12</sup>C L-methionine. Specifically, mass spectrometry analysis reveals that the isotopic fractionation of both natural and ¹³C-enriched L-methionine is influenced by electron spin-dependent interactions.</div></div><div>Distinct isotopic fractionation in biomolecules, compared with atmospheric values, reflects their biosynthetic origin. Monitoring these fractionation changes offers a valuable approach for probing early metabolic networks. A key question in the study of life’s origins is the role of electronic spin and magnetic surfaces in symmetry breaking and the emergence of homochirality. Here, we used magnetic filters to show that the dynamical interaction with the magnetic surfaces changes the isotope fractions ","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 102993"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507696","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 : 2026-10-08Epub Date: 2026-05-08DOI: 10.1016/j.chempr.2026.103059
Yuyao Kuang, Ze-Fan Yao, Sydney To, Sheng Wei Tang, Joni Spencer, Ronald Dat Phung, Hao-Tian Wu, Catherine Salgado, Li Xing, Karolina Sulowska, Joanna Olesiak-Bańska, Jian Pei, Elizabeth M.Y. Lee, Herdeline Ann M. Ardoña
<div><ul><li><span>•</span><span><div>Morphological fates could be driven by torsional mismatch between supramolecular units</div></span></li><li><span>•</span><span><div>Coassembly shows non-additive nanostructure and local chirality</div></span></li><li><span>•</span><span><div>Divergence in assembly interactions yields variations in optoelectronic functions</div></span></li></ul></div><div>The molecular design of organic electronic materials dictates their hierarchical assembly structure and functional properties, often governing their emergent behavior, especially when they are interfaced with living systems. When π-conjugated units are incorporated into biomolecular networks such as peptide structures, geometric constraints and supramolecular interactions introduce additional complexity to conventional biomolecular assemblies and make structure-property relationships more difficult to predict. Here, we show that torsional mismatch between peptide-functionalized donor and acceptor π-conjugated units can serve as a simple yet powerful design parameter to expand the range of accessible nanostructures and functional properties for a water-processable supramolecular bioelectronic system. Utilizing a sequence-matched peptide system bearing a flexible donor and a rigid acceptor, we demonstrated that each component assembles into distinct structures individually, whereas combining them produces hybrid morphologies, distinct from nanostructures achieved by mixing the separately assembled donor and acceptor units. The resulting coassembled structures exhibit altered chirality and dimensionality, which are more than the sum of their individual components and have an influence on energy-transfer behavior and photocurrent generation of the bulk material. We further demonstrate that assembly pathways, such as thermal annealing and acidification kinetics, can direct the system into different local minima, which enables dynamic control over morphology and function without changing molecular composition. Together, these findings highlight an approach that leverages geometric mismatch and pathway dependence to access diverse assembly structures and functional states for a bioelectronic system, thus establishing a generalizable strategy for designing adaptive, water-processable biomacromolecules with molecularly tunable optoelectronic properties.</div><div><div>Sequence-defined hierarchical structure critically governs the function and emergent properties of biomacromolecules. However, introducing functional yet bulky π-conjugated synthetic units imposes geometric constraints that complicate the rational prediction of structure-morphology correlations for engineered biomacromolecules. Here, we report an intriguing coassembly behavior of a sequence-matched peptide pair bearing energy-transporting π-electron donor/acceptor cores (triaspartic acid [DDD]-quaterthiophene [4T]/DDD-perylene diimide [PDI]). Individually, DDD-4T forms twisted 1D chiral nanofibers, wher
{"title":"Geometric divergence in nanostructural fates of coassembled peptides leads to broadening of morphology-based optoelectronic property outcomes","authors":"Yuyao Kuang, Ze-Fan Yao, Sydney To, Sheng Wei Tang, Joni Spencer, Ronald Dat Phung, Hao-Tian Wu, Catherine Salgado, Li Xing, Karolina Sulowska, Joanna Olesiak-Bańska, Jian Pei, Elizabeth M.Y. Lee, Herdeline Ann M. Ardoña","doi":"10.1016/j.chempr.2026.103059","DOIUrl":"10.1016/j.chempr.2026.103059","url":null,"abstract":"<div><ul><li><span>•</span><span><div>Morphological fates could be driven by torsional mismatch between supramolecular units</div></span></li><li><span>•</span><span><div>Coassembly shows non-additive nanostructure and local chirality</div></span></li><li><span>•</span><span><div>Divergence in assembly interactions yields variations in optoelectronic functions</div></span></li></ul></div><div>The molecular design of organic electronic materials dictates their hierarchical assembly structure and functional properties, often governing their emergent behavior, especially when they are interfaced with living systems. When π-conjugated units are incorporated into biomolecular networks such as peptide structures, geometric constraints and supramolecular interactions introduce additional complexity to conventional biomolecular assemblies and make structure-property relationships more difficult to predict. Here, we show that torsional mismatch between peptide-functionalized donor and acceptor π-conjugated units can serve as a simple yet powerful design parameter to expand the range of accessible nanostructures and functional properties for a water-processable supramolecular bioelectronic system. Utilizing a sequence-matched peptide system bearing a flexible donor and a rigid acceptor, we demonstrated that each component assembles into distinct structures individually, whereas combining them produces hybrid morphologies, distinct from nanostructures achieved by mixing the separately assembled donor and acceptor units. The resulting coassembled structures exhibit altered chirality and dimensionality, which are more than the sum of their individual components and have an influence on energy-transfer behavior and photocurrent generation of the bulk material. We further demonstrate that assembly pathways, such as thermal annealing and acidification kinetics, can direct the system into different local minima, which enables dynamic control over morphology and function without changing molecular composition. Together, these findings highlight an approach that leverages geometric mismatch and pathway dependence to access diverse assembly structures and functional states for a bioelectronic system, thus establishing a generalizable strategy for designing adaptive, water-processable biomacromolecules with molecularly tunable optoelectronic properties.</div><div><div>Sequence-defined hierarchical structure critically governs the function and emergent properties of biomacromolecules. However, introducing functional yet bulky π-conjugated synthetic units imposes geometric constraints that complicate the rational prediction of structure-morphology correlations for engineered biomacromolecules. Here, we report an intriguing coassembly behavior of a sequence-matched peptide pair bearing energy-transporting π-electron donor/acceptor cores (triaspartic acid [DDD]-quaterthiophene [4T]/DDD-perylene diimide [PDI]). Individually, DDD-4T forms twisted 1D chiral nanofibers, wher","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 103059"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13577602/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148979347","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-08DOI: 10.1016/j.chempr.2026.103216
Wenhao Ren, Shi-Zhang Qiao
The stable production of concentrated formate remains a major challenge in CO2 electrolysis. A recent Nature Catalysis study by Lu et al. reports a high-flux membrane electrode assembly design that replaces the conventional carbon-fiber gas diffusion electrode with a highly porous copper foam, enabling continuous production of 4.5 M formate at ∼90% Faradaic efficiency for over 8,000 h.
The stable production of concentrated formate remains a major challenge in CO2 electrolysis. A recent Nature Catalysis study by Lu et al. reports a high-flux membrane electrode assembly design that replaces the conventional carbon-fiber gas diffusion electrode with a highly porous copper foam, enabling continuous production of 4.5 M formate at ∼90% Faradaic efficiency for over 8,000 h.
{"title":"A high-flux cathode for stable and scalable CO2 electroreduction to concentrated formate","authors":"Wenhao Ren, Shi-Zhang Qiao","doi":"10.1016/j.chempr.2026.103216","DOIUrl":"10.1016/j.chempr.2026.103216","url":null,"abstract":"<div><div>The stable production of concentrated formate remains a major challenge in CO<sub>2</sub> electrolysis. A recent <em>Nature Catalysis</em> study by Lu et al. reports a high-flux membrane electrode assembly design that replaces the conventional carbon-fiber gas diffusion electrode with a highly porous copper foam, enabling continuous production of 4.5 M formate at ∼90% Faradaic efficiency for over 8,000 h.</div></div><div>The stable production of concentrated formate remains a major challenge in CO<sub>2</sub> electrolysis. A recent <em>Nature Catalysis</em> study by Lu et al. reports a high-flux membrane electrode assembly design that replaces the conventional carbon-fiber gas diffusion electrode with a highly porous copper foam, enabling continuous production of 4.5 M formate at ∼90% Faradaic efficiency for over 8,000 h.</div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 103216"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124082","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}
<div>The activation of chemical oxidants to generate highly reactive species lies at the heart of numerous technologies crucial for a sustainable future, from purifying polluted water sources to driving selective chemical transformations under mild conditions. However, steering this powerful chemistry toward a desired reaction pathway—whether to produce a specific radical for unselective degradation or a non-radical species for precise synthesis—remains a grand challenge. Single-atom catalysis, by offering a platform to design active sites with atomic precision, provides an unprecedented opportunity to tackle this challenge. This review bridges the gap between fundamental mechanistic understanding and practical catalyst design. By deconstructing how the local environment of an isolated metal atom dictates the nature of the reactive species formed, we chart a roadmap for creating catalysts with tailored reactivity. This knowledge not only promises to revolutionize the efficiency and selectivity of water treatment technologies but also opens new avenues for sustainable chemical manufacturing, aligning with the principles of green chemistry and contributing to a circular economy. Ultimately, mastering the art of tuning reactive species in single-atom catalysts (SACs) is a critical step toward harnessing the full potential of advanced oxidation processes (AOPs) for environmental protection and beyond.</div><div><div>Precise control over the reactive species generated in oxidant activation systems—specifically hydroxyl radicals (<sup>⋅</sup>OH), sulfate radicals (SO<sub>4</sub><sup>⋅–</sup>), singlet oxygen (<sup>1</sup>O<sub>2</sub>), and high-valent metal-oxo (HVMO) species—is of paramount importance for advancing environmental remediation and selective oxidation. Single-atom catalysts (SACs) have emerged as a powerful and tunable platform to govern this process at the atomic scale. This review systematically elucidates the fundamental mechanisms governing reactive species generation at isolated metal sites, focusing on the key processes of oxidant adsorption, electron transfer, and intermediate transformation. We critically analyze how these elementary steps dictate selective production of target radical and non-radical reactive species and comprehensively discuss the state-of-the-art design strategies—including coordination engineering, defect modulation, and bimetallic site construction—that enable the rational manipulation of these pathways. Finally, we provide a forward-looking perspective on challenges and opportunities, guiding the development of next-generation SACs for sustainable oxidation processes.</div></div><div>Precise control over the reactive species generated in oxidant activation systems—specifically hydroxyl radicals (<sup>⋅</sup>OH), sulfate radicals (SO<sub>4</sub><sup>⋅–</sup>), singlet oxygen (<sup>1</sup>O<sub>2</sub>), and high-valent metal-oxo (HVMO) species—is of paramount importance for advancing environmental remediatio
{"title":"Tuning the reactive species in oxidant activation by single-atom catalysts: Mechanisms, manipulations, and perspectives","authors":"Qi Fu, Boyuan Hao, Minling Qin, Bang Lan, Fang Zhu, Junhui Wang, Zhengping Hao, Gangfeng Ouyang","doi":"10.1016/j.chempr.2026.103192","DOIUrl":"10.1016/j.chempr.2026.103192","url":null,"abstract":"<div>The activation of chemical oxidants to generate highly reactive species lies at the heart of numerous technologies crucial for a sustainable future, from purifying polluted water sources to driving selective chemical transformations under mild conditions. However, steering this powerful chemistry toward a desired reaction pathway—whether to produce a specific radical for unselective degradation or a non-radical species for precise synthesis—remains a grand challenge. Single-atom catalysis, by offering a platform to design active sites with atomic precision, provides an unprecedented opportunity to tackle this challenge. This review bridges the gap between fundamental mechanistic understanding and practical catalyst design. By deconstructing how the local environment of an isolated metal atom dictates the nature of the reactive species formed, we chart a roadmap for creating catalysts with tailored reactivity. This knowledge not only promises to revolutionize the efficiency and selectivity of water treatment technologies but also opens new avenues for sustainable chemical manufacturing, aligning with the principles of green chemistry and contributing to a circular economy. Ultimately, mastering the art of tuning reactive species in single-atom catalysts (SACs) is a critical step toward harnessing the full potential of advanced oxidation processes (AOPs) for environmental protection and beyond.</div><div><div>Precise control over the reactive species generated in oxidant activation systems—specifically hydroxyl radicals (<sup>⋅</sup>OH), sulfate radicals (SO<sub>4</sub><sup>⋅–</sup>), singlet oxygen (<sup>1</sup>O<sub>2</sub>), and high-valent metal-oxo (HVMO) species—is of paramount importance for advancing environmental remediation and selective oxidation. Single-atom catalysts (SACs) have emerged as a powerful and tunable platform to govern this process at the atomic scale. This review systematically elucidates the fundamental mechanisms governing reactive species generation at isolated metal sites, focusing on the key processes of oxidant adsorption, electron transfer, and intermediate transformation. We critically analyze how these elementary steps dictate selective production of target radical and non-radical reactive species and comprehensively discuss the state-of-the-art design strategies—including coordination engineering, defect modulation, and bimetallic site construction—that enable the rational manipulation of these pathways. Finally, we provide a forward-looking perspective on challenges and opportunities, guiding the development of next-generation SACs for sustainable oxidation processes.</div></div><div>Precise control over the reactive species generated in oxidant activation systems—specifically hydroxyl radicals (<sup>⋅</sup>OH), sulfate radicals (SO<sub>4</sub><sup>⋅–</sup>), singlet oxygen (<sup>1</sup>O<sub>2</sub>), and high-valent metal-oxo (HVMO) species—is of paramount importance for advancing environmental remediatio","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 103192"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148756630","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 : 2026-10-08Epub Date: 2026-05-28DOI: 10.1016/j.chempr.2026.103076
Andreas Ostertag, Suman Dana, Christof Sparr
<div><ul><li><span>•</span><span><div>Discovery and isolation of C–P atropisomers</div></span></li><li><span>•</span><span><div>High configurational stability and threefold stereogenicity</div></span></li><li><span>•</span><span><div>Regio-, diastereo-, and enantiocontrol of C–P atropisomers by catalytic C–H activation</div></span></li><li><span>•</span><span><div>Application of C–P atropisomers for absolute configuration determination</div></span></li></ul></div><div>Chiral organophosphorus compounds with defined relative and absolute configuration have evolved into a mainstay in synthesis and catalysis. However, besides systems with a chiral backbone, <em>P</em>-stereocenters remained the only configurationally stable stereogenic unit based on phosphorus. The properties of the stereoisomers with <em>P</em>-stereocenters, their stereoselective synthesis, and their diverse applications were investigated in detail. Nevertheless, despite the numerous functionalities based on the C–P bond, isomers resulting from the restricted rotation about the C–P bond have not yet been described. In contrast, the immense range of atropisomers with high rotational barriers about the C–C or C–N bonds advanced to a cornerstone of stereochemistry. Owing to their longer bond lengths and higher flexibility, only C–S and C–I bonds have been established as configurationally stable stereogenic axes with elements beyond the second row. Given their significance in organic chemistry, we evaluated the viability to halt the rotation about the C–P bond. We discovered that triptycyl phosphine oxides with threefold stereogenic C–P axes feature rotational barriers sufficiently high to separate C–P atropisomers under ambient conditions. Furthermore, a regio- and diastereoselective synthesis was developed to catalytically control the configuration of C–P atropisomers via a Fujiwara-Moritani reaction, and the feasibility of enantiocontrol was confirmed. Given the diversity of organophosphorus chemistry, it is expected that the atropisomerism at the C–P bond and the stereoselective synthesis of configurationally stable C–P atropisomers will enable the preparation of structurally well-defined molecular architectures to advance reaction development, ligand design, catalysis, and the assembly of functional systems.</div><div><div>The feasibility of halting the rotation about a C–P bond is reported. At the outset, atropisomers with configurationally stable stereogenic C–P axes were synthesized in the form of triptycyl phosphine oxides with threefold stereogenicity. Their bond rotational profile revealed that each of the three barriers amounts to more than 115 kJ/mol, which permits the isolation of the antiperiplanar and the two enantiomeric synclinal C–P atropisomers under ambient conditions. Furthermore, the feasibility of their atroposelective synthesis by desymmetrization was established to catalytically control the configuration of stereogenic C–P axes. A first application of the synt
{"title":"Atropisomerism at the carbon–phosphorus bond","authors":"Andreas Ostertag, Suman Dana, Christof Sparr","doi":"10.1016/j.chempr.2026.103076","DOIUrl":"10.1016/j.chempr.2026.103076","url":null,"abstract":"<div><ul><li><span>•</span><span><div>Discovery and isolation of C–P atropisomers</div></span></li><li><span>•</span><span><div>High configurational stability and threefold stereogenicity</div></span></li><li><span>•</span><span><div>Regio-, diastereo-, and enantiocontrol of C–P atropisomers by catalytic C–H activation</div></span></li><li><span>•</span><span><div>Application of C–P atropisomers for absolute configuration determination</div></span></li></ul></div><div>Chiral organophosphorus compounds with defined relative and absolute configuration have evolved into a mainstay in synthesis and catalysis. However, besides systems with a chiral backbone, <em>P</em>-stereocenters remained the only configurationally stable stereogenic unit based on phosphorus. The properties of the stereoisomers with <em>P</em>-stereocenters, their stereoselective synthesis, and their diverse applications were investigated in detail. Nevertheless, despite the numerous functionalities based on the C–P bond, isomers resulting from the restricted rotation about the C–P bond have not yet been described. In contrast, the immense range of atropisomers with high rotational barriers about the C–C or C–N bonds advanced to a cornerstone of stereochemistry. Owing to their longer bond lengths and higher flexibility, only C–S and C–I bonds have been established as configurationally stable stereogenic axes with elements beyond the second row. Given their significance in organic chemistry, we evaluated the viability to halt the rotation about the C–P bond. We discovered that triptycyl phosphine oxides with threefold stereogenic C–P axes feature rotational barriers sufficiently high to separate C–P atropisomers under ambient conditions. Furthermore, a regio- and diastereoselective synthesis was developed to catalytically control the configuration of C–P atropisomers via a Fujiwara-Moritani reaction, and the feasibility of enantiocontrol was confirmed. Given the diversity of organophosphorus chemistry, it is expected that the atropisomerism at the C–P bond and the stereoselective synthesis of configurationally stable C–P atropisomers will enable the preparation of structurally well-defined molecular architectures to advance reaction development, ligand design, catalysis, and the assembly of functional systems.</div><div><div>The feasibility of halting the rotation about a C–P bond is reported. At the outset, atropisomers with configurationally stable stereogenic C–P axes were synthesized in the form of triptycyl phosphine oxides with threefold stereogenicity. Their bond rotational profile revealed that each of the three barriers amounts to more than 115 kJ/mol, which permits the isolation of the antiperiplanar and the two enantiomeric synclinal C–P atropisomers under ambient conditions. Furthermore, the feasibility of their atroposelective synthesis by desymmetrization was established to catalytically control the configuration of stereogenic C–P axes. A first application of the synt","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 103076"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149125239","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-08DOI: 10.1016/j.chempr.2026.103295
Shengqian Ma
A lover of travel and cooking, Shengqian Ma overcame career challenges by pioneering research grounded in extensive reading, critical thinking, and creativity. He advises young scientists to embrace passion, patience, perseverance, and problem-driven ambition. His teaching and mentorship foster independence and motivation. He anticipates transformative chemistry enabled by artificial intelligence and values Chem’s selective approach to publishing.
A lover of travel and cooking, Shengqian Ma overcame career challenges by pioneering research grounded in extensive reading, critical thinking, and creativity. He advises young scientists to embrace passion, patience, perseverance, and problem-driven ambition. His teaching and mentorship foster independence and motivation. He anticipates transformative chemistry enabled by artificial intelligence and values Chem’s selective approach to publishing.
{"title":"Chem at 10: Shengqian Ma","authors":"Shengqian Ma","doi":"10.1016/j.chempr.2026.103295","DOIUrl":"10.1016/j.chempr.2026.103295","url":null,"abstract":"<div><div>A lover of travel and cooking, Shengqian Ma overcame career challenges by pioneering research grounded in extensive reading, critical thinking, and creativity. He advises young scientists to embrace passion, patience, perseverance, and problem-driven ambition. His teaching and mentorship foster independence and motivation. He anticipates transformative chemistry enabled by artificial intelligence and values <em>Chem</em>’s selective approach to publishing.</div></div><div>A lover of travel and cooking, Shengqian Ma overcame career challenges by pioneering research grounded in extensive reading, critical thinking, and creativity. He advises young scientists to embrace passion, patience, perseverance, and problem-driven ambition. His teaching and mentorship foster independence and motivation. He anticipates transformative chemistry enabled by artificial intelligence and values <em>Chem</em>’s selective approach to publishing.</div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 103295"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149124087","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-10-08Epub Date: 2026-03-30DOI: 10.1016/j.chempr.2026.103004
Nilangshu Mandal, Guanqi Qiu
<div><ul><li><span>•</span><span><div>Dispersion reshapes kinetic-thermodynamic responsiveness</div></span></li><li><span>•</span><span><div>Responsiveness changed by both direct and geometry-mediated dispersion interactions</div></span></li><li><span>•</span><span><div>Selectivity trends prediction requires considering kinetic-thermodynamic responsiveness</div></span></li><li><span>•</span><span><div>Dispersion interactions enhance selectivity robustness across substrates</div></span></li></ul></div><div>Chemical reactivity is often described in terms of how high or low the activation energy is. Yet equally important is how that barrier responds when thermodynamic driving forces change. The sensitivity of a reaction to such changes determines selectivity, robustness, and tunability across chemical space. While London dispersion (LD) interactions are widely recognized for stabilizing molecular structures and lowering reaction barriers, their influence on intrinsic reactivity parameters has not been systematically examined. Here, we show that LD does more than shift barrier heights. It modulates the thermodynamically independent components of reactivity, thereby altering how barriers respond to thermodynamic perturbations. In other words, dispersion changes not only <em>how low</em> a barrier is, but <em>how responsive</em> it is. By isolating thermodynamically independent contributions to activation free energies, we reframe dispersion as an active design parameter rather than a snapshot stabilizing force. This conceptual shift opens new possibilities for engineering reaction landscapes: instead of merely lowering barriers, one can tune the sensitivity of a reaction to driving force, potentially enabling improved selectivity and control. More broadly, our findings suggest that familiar non-covalent interactions may have underexplored roles in shaping kinetic-thermodynamic responsiveness, encouraging a more causally explicit approach to reactivity design.</div><div><div>While London dispersion (LD) is widely recognized for lowering reaction barriers, we show that it also modulates how barriers respond to thermodynamic driving force, representing a conceptual shift from absolute effects to system-level responsiveness. Here we show that LD modulates the Brønsted slope (α), a key measure of kinetic-thermodynamic responsiveness (ΔΔ<em>G</em><sup>‡</sup>/ΔΔ<em>G</em>), revealing effects beyond simple barrier stabilization. Structural analyses further show that LD influences responsiveness both directly and through secondary effects, including changes in geometry and additional non-covalent interactions along the reaction coordinate. By conceptually isolating the thermodynamically independent consequences of LD, we establish dispersion as an active, tunable lever for modulating responsiveness. This reframing enables clearer distinctions between case-specific and systematic effects. We also demonstrate that accounting for this responsiveness is essential
{"title":"From absolute barriers to responsiveness: How London dispersion modulates kinetic-thermodynamic relationships","authors":"Nilangshu Mandal, Guanqi Qiu","doi":"10.1016/j.chempr.2026.103004","DOIUrl":"10.1016/j.chempr.2026.103004","url":null,"abstract":"<div><ul><li><span>•</span><span><div>Dispersion reshapes kinetic-thermodynamic responsiveness</div></span></li><li><span>•</span><span><div>Responsiveness changed by both direct and geometry-mediated dispersion interactions</div></span></li><li><span>•</span><span><div>Selectivity trends prediction requires considering kinetic-thermodynamic responsiveness</div></span></li><li><span>•</span><span><div>Dispersion interactions enhance selectivity robustness across substrates</div></span></li></ul></div><div>Chemical reactivity is often described in terms of how high or low the activation energy is. Yet equally important is how that barrier responds when thermodynamic driving forces change. The sensitivity of a reaction to such changes determines selectivity, robustness, and tunability across chemical space. While London dispersion (LD) interactions are widely recognized for stabilizing molecular structures and lowering reaction barriers, their influence on intrinsic reactivity parameters has not been systematically examined. Here, we show that LD does more than shift barrier heights. It modulates the thermodynamically independent components of reactivity, thereby altering how barriers respond to thermodynamic perturbations. In other words, dispersion changes not only <em>how low</em> a barrier is, but <em>how responsive</em> it is. By isolating thermodynamically independent contributions to activation free energies, we reframe dispersion as an active design parameter rather than a snapshot stabilizing force. This conceptual shift opens new possibilities for engineering reaction landscapes: instead of merely lowering barriers, one can tune the sensitivity of a reaction to driving force, potentially enabling improved selectivity and control. More broadly, our findings suggest that familiar non-covalent interactions may have underexplored roles in shaping kinetic-thermodynamic responsiveness, encouraging a more causally explicit approach to reactivity design.</div><div><div>While London dispersion (LD) is widely recognized for lowering reaction barriers, we show that it also modulates how barriers respond to thermodynamic driving force, representing a conceptual shift from absolute effects to system-level responsiveness. Here we show that LD modulates the Brønsted slope (α), a key measure of kinetic-thermodynamic responsiveness (ΔΔ<em>G</em><sup>‡</sup>/ΔΔ<em>G</em>), revealing effects beyond simple barrier stabilization. Structural analyses further show that LD influences responsiveness both directly and through secondary effects, including changes in geometry and additional non-covalent interactions along the reaction coordinate. By conceptually isolating the thermodynamically independent consequences of LD, we establish dispersion as an active, tunable lever for modulating responsiveness. This reframing enables clearer distinctions between case-specific and systematic effects. We also demonstrate that accounting for this responsiveness is essential","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 103004"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147577716","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
<div><ul><li><span>•</span><span><div>A novel descriptor is proposed to predict the stability and activity of bimetallic sites</div></span></li><li><span>•</span><span><div>The Cr-Fe bimetallic site is identified as exhibiting superior activity and stability</div></span></li><li><span>•</span><span><div>The as-synthesized Cr/Fe-NC shows an anti-dissolving capacity in electrochemical tests</div></span></li></ul></div><div>The instability of Fe-based single-atom catalysts in acidic media remains a major obstacle to the practical realization of platinum-group-metal-free proton exchange membrane fuel cells. Moving beyond empirical optimization, we establish a quantitative structural descriptor (φ) that enables the predictive screening of both the activity and the durability of Fe-based dual-atom sites. Guided by φ, the Cr-Fe motif is identified as an intrinsically stable configuration, wherein the Cr atom electronically stabilizes the Fe center against dissolution. The resulting Cr/Fe-NC catalyst serves as a proof of concept for the descriptor-driven design of dissolution-resistant active sites. More broadly, this approach offers a transferable framework for the stabilization of atomic-level active centers in acidic environments, paving the way for durable non-precious metal catalysts in energy conversion and storage technologies.</div><div><div>Atomic Fe-based catalysts are promising cathode alternatives to Pt-based materials in proton exchange membrane fuel cells (PEMFCs) toward the oxygen reduction reaction (ORR), yet they suffer from substantial activity degradation during operation. By constructing a novel theoretical descriptor to evaluate the metal dissolution energy (<em>U</em><sub>diss</sub>) and ∗OH adsorption energy (ΔG<sub>OH</sub>), we transcend the bottleneck of the conventional trial-and-error strategy for Fe-M bimetallic atomic sites (BASs) and screen Cr-Fe as the optimal combination, exhibiting the highest <em>U</em><sub>diss</sub> and suitable ΔG<sub>OH</sub> for high ORR performance. The developed Cr-Fe BASs in N-doped carbon catalysts exhibit a substantially improved stability in PEMFCs, demonstrating over 55% retention of the initial current (from ca. 410 to 220 mA cm<sup>−2</sup>) after 210 h, compared with the state-of-the-art Fe single-atom catalysts (SACs). This work provides valuable insights into advancing non-precious metal catalysts for PEMFCs, bringing their commercialization one step closer.</div></div><div>Atomic Fe-based catalysts are promising cathode alternatives to Pt-based materials in proton exchange membrane fuel cells (PEMFCs) toward the oxygen reduction reaction (ORR), yet they suffer from substantial activity degradation during operation. By constructing a novel theoretical descriptor to evaluate the metal dissolution energy (<em>U</em><sub>diss</sub>) and ∗OH adsorption energy (ΔG<sub>OH</sub>), we transcend the bottleneck of the conventional trial-and-error strategy for Fe-M bimetallic atomic sites (BASs) a
原子铁基催化剂是质子交换膜燃料电池（pemfc）中氧还原反应（ORR）的极具前景的阴极替代品，但其在运行过程中存在严重的活性降低问题。通过构建新的理论描述符来评估金属溶解能（Udiss）和* OH吸附能（ΔGOH），我们突破了Fe-M双金属原子位（BASs）的传统试错策略的瓶颈，筛选出Cr-Fe作为最佳组合，具有最高的Udiss和适合ΔGOH的高ORR性能。与最先进的Fe单原子催化剂（SACs）相比，在n掺杂碳催化剂中开发的Cr-Fe BASs在pemfc中表现出显著提高的稳定性，在210小时后，其初始电流（从约410 mA cm - 2到220 mA cm - 2）的保留率超过55%。这项工作为推进pemfc的非贵金属催化剂提供了有价值的见解，使其商业化更进一步。
{"title":"Screening, designing, and elucidating anti-dissolving dual atomic sites for highly durable proton exchange membrane fuel cells","authors":"Jingwen Wang, Hongye Wang, Linjie Zhao, Yongming Xia, Xian Liang, Lipeng Zhang, Baoguang Mao, Lin Yang, Dong Liu, Yuqin Jiang, Zhengyu Bai, Zhongwei Chen, Chuangang Hu","doi":"10.1016/j.chempr.2026.103007","DOIUrl":"10.1016/j.chempr.2026.103007","url":null,"abstract":"<div><ul><li><span>•</span><span><div>A novel descriptor is proposed to predict the stability and activity of bimetallic sites</div></span></li><li><span>•</span><span><div>The Cr-Fe bimetallic site is identified as exhibiting superior activity and stability</div></span></li><li><span>•</span><span><div>The as-synthesized Cr/Fe-NC shows an anti-dissolving capacity in electrochemical tests</div></span></li></ul></div><div>The instability of Fe-based single-atom catalysts in acidic media remains a major obstacle to the practical realization of platinum-group-metal-free proton exchange membrane fuel cells. Moving beyond empirical optimization, we establish a quantitative structural descriptor (φ) that enables the predictive screening of both the activity and the durability of Fe-based dual-atom sites. Guided by φ, the Cr-Fe motif is identified as an intrinsically stable configuration, wherein the Cr atom electronically stabilizes the Fe center against dissolution. The resulting Cr/Fe-NC catalyst serves as a proof of concept for the descriptor-driven design of dissolution-resistant active sites. More broadly, this approach offers a transferable framework for the stabilization of atomic-level active centers in acidic environments, paving the way for durable non-precious metal catalysts in energy conversion and storage technologies.</div><div><div>Atomic Fe-based catalysts are promising cathode alternatives to Pt-based materials in proton exchange membrane fuel cells (PEMFCs) toward the oxygen reduction reaction (ORR), yet they suffer from substantial activity degradation during operation. By constructing a novel theoretical descriptor to evaluate the metal dissolution energy (<em>U</em><sub>diss</sub>) and ∗OH adsorption energy (ΔG<sub>OH</sub>), we transcend the bottleneck of the conventional trial-and-error strategy for Fe-M bimetallic atomic sites (BASs) and screen Cr-Fe as the optimal combination, exhibiting the highest <em>U</em><sub>diss</sub> and suitable ΔG<sub>OH</sub> for high ORR performance. The developed Cr-Fe BASs in N-doped carbon catalysts exhibit a substantially improved stability in PEMFCs, demonstrating over 55% retention of the initial current (from ca. 410 to 220 mA cm<sup>−2</sup>) after 210 h, compared with the state-of-the-art Fe single-atom catalysts (SACs). This work provides valuable insights into advancing non-precious metal catalysts for PEMFCs, bringing their commercialization one step closer.</div></div><div>Atomic Fe-based catalysts are promising cathode alternatives to Pt-based materials in proton exchange membrane fuel cells (PEMFCs) toward the oxygen reduction reaction (ORR), yet they suffer from substantial activity degradation during operation. By constructing a novel theoretical descriptor to evaluate the metal dissolution energy (<em>U</em><sub>diss</sub>) and ∗OH adsorption energy (ΔG<sub>OH</sub>), we transcend the bottleneck of the conventional trial-and-error strategy for Fe-M bimetallic atomic sites (BASs) a","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 103007"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147586176","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 : 2026-10-08Epub Date: 2026-04-23DOI: 10.1016/j.chempr.2026.103043
Hyeong Seok Kim, Nirvana T. Almada, Elizabeth A. Recker, Seth R. Allen, Jaechul Ju, Connor J. O’Dea, Benjamin S. Saada, Madison G. Handojo, Kathleen N. Halwachs, Adrianne M. Rosales, Sean T. Roberts, Zachariah A. Page
<div><ul><li><span>•</span><span><div>Oxygen-tolerant type-I photoinitiators activated by low-intensity green LEDs</div></span></li><li><span>•</span><span><div>Ethyl substitution yields 10× shorter inhibition times and ∼2× faster polymerizations</div></span></li><li><span>•</span><span><div>Spectroscopy confirms enhanced efficiency and selectivity for ethyl radical formation</div></span></li><li><span>•</span><span><div>Proof-of-concept ambient 3D printing with 2.5 s exposures at 3 mW cm<sup>−2</sup> intensity</div></span></li></ul></div><div>Type I photoinitiators generate radicals through light-induced homolytic bond cleavage, which has enabled photopolymerization processes used across the coatings, microelectronics, and 3D printing industries. However, most rely on ultraviolet (UV) light, which limits safety, reaction depth, and compatibility with sensitive materials. Visible-light systems offer milder activation and deeper light penetration but remain constrained by a narrow chemical scope and oxygen inhibition. To address these challenges, recent designs, such as acylgermanes and silyl ketones, have extended absorption to blue light. Building on this foundation, this work establishes boron-alkylated BODIPYs as a new class of oxygen-tolerant, visible-light type I photoinitiators operating efficiently under green light. Exchanging methyl substitution at boron for ethyl groups was found to dramatically lower the B–C bond dissociation energy, accelerate photolysis, and mitigate oxygen quenching, enabling rapid polymerization and open-air 3D printing of commercial acrylics. The modular BODIPY framework allows for the rational tuning of excited-state dynamics and photolysis efficiency through systematic boron substitution. Looking forward, extending these design rules could yield more efficient, longer-wavelength, and biocompatible initiators for additive manufacturing, dental curing, and tissue engineering, representing a step toward safer and more energy-conscious light-driven technologies.</div><div><div>Conventional type I photoinitiators require high-energy ultraviolet (UV) light to generate radicals, whereas most visible-light systems rely on slower, oxygen-sensitive type II photosensitization pathways. We report boron-alkylated boron-dipyrromethenes (BODIPYs) as type I photoinitiators that operate efficiently under green-light-emitting diodes (LEDs) and ambient conditions. Replacing methyl with ethyl at the boron site accelerates photolysis, lowers the B–C bond dissociation energy, and suppresses oxygen sensitization. Consequently, the ethyl derivative doubles the polymerization rate and decreases oxygen inhibition times by over an order of magnitude. Relative to Ivocerin, a leading blue-light type I photoinitiator, the BODIPY system achieves a higher external quantum yield due to stronger absorption. Owing to these performance enhancements, the ethyl derivative enables rapid, ambient, green-light digital light processing (DLP) 3D printing
{"title":"Oxygen-tolerant green-light photopolymerizations with type I boron-alkylated BODIPYs: The power of a methylene","authors":"Hyeong Seok Kim, Nirvana T. Almada, Elizabeth A. Recker, Seth R. Allen, Jaechul Ju, Connor J. O’Dea, Benjamin S. Saada, Madison G. Handojo, Kathleen N. Halwachs, Adrianne M. Rosales, Sean T. Roberts, Zachariah A. Page","doi":"10.1016/j.chempr.2026.103043","DOIUrl":"10.1016/j.chempr.2026.103043","url":null,"abstract":"<div><ul><li><span>•</span><span><div>Oxygen-tolerant type-I photoinitiators activated by low-intensity green LEDs</div></span></li><li><span>•</span><span><div>Ethyl substitution yields 10× shorter inhibition times and ∼2× faster polymerizations</div></span></li><li><span>•</span><span><div>Spectroscopy confirms enhanced efficiency and selectivity for ethyl radical formation</div></span></li><li><span>•</span><span><div>Proof-of-concept ambient 3D printing with 2.5 s exposures at 3 mW cm<sup>−2</sup> intensity</div></span></li></ul></div><div>Type I photoinitiators generate radicals through light-induced homolytic bond cleavage, which has enabled photopolymerization processes used across the coatings, microelectronics, and 3D printing industries. However, most rely on ultraviolet (UV) light, which limits safety, reaction depth, and compatibility with sensitive materials. Visible-light systems offer milder activation and deeper light penetration but remain constrained by a narrow chemical scope and oxygen inhibition. To address these challenges, recent designs, such as acylgermanes and silyl ketones, have extended absorption to blue light. Building on this foundation, this work establishes boron-alkylated BODIPYs as a new class of oxygen-tolerant, visible-light type I photoinitiators operating efficiently under green light. Exchanging methyl substitution at boron for ethyl groups was found to dramatically lower the B–C bond dissociation energy, accelerate photolysis, and mitigate oxygen quenching, enabling rapid polymerization and open-air 3D printing of commercial acrylics. The modular BODIPY framework allows for the rational tuning of excited-state dynamics and photolysis efficiency through systematic boron substitution. Looking forward, extending these design rules could yield more efficient, longer-wavelength, and biocompatible initiators for additive manufacturing, dental curing, and tissue engineering, representing a step toward safer and more energy-conscious light-driven technologies.</div><div><div>Conventional type I photoinitiators require high-energy ultraviolet (UV) light to generate radicals, whereas most visible-light systems rely on slower, oxygen-sensitive type II photosensitization pathways. We report boron-alkylated boron-dipyrromethenes (BODIPYs) as type I photoinitiators that operate efficiently under green-light-emitting diodes (LEDs) and ambient conditions. Replacing methyl with ethyl at the boron site accelerates photolysis, lowers the B–C bond dissociation energy, and suppresses oxygen sensitization. Consequently, the ethyl derivative doubles the polymerization rate and decreases oxygen inhibition times by over an order of magnitude. Relative to Ivocerin, a leading blue-light type I photoinitiator, the BODIPY system achieves a higher external quantum yield due to stronger absorption. Owing to these performance enhancements, the ethyl derivative enables rapid, ambient, green-light digital light processing (DLP) 3D printing","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 10","pages":"Article 103043"},"PeriodicalIF":19.1,"publicationDate":"2026-10-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148979335","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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