Pub Date : 2025-03-13DOI: 10.1016/j.chempr.2025.102433
Zhongtao Feng , Rei Kinjo
In this issue of Chem, Braunschweig et al. report the selective synthesis of an electron-precise tetra(amino)tetraborane featuring a puckered B4 ring. Chemical redox reactions lead to the stable radical anion, dianion, and radical cation. The four charge states of the B4 ring are poised to spark a revolution in boron chemistry.
{"title":"Redox chemistry of cyclotetraborane","authors":"Zhongtao Feng , Rei Kinjo","doi":"10.1016/j.chempr.2025.102433","DOIUrl":"10.1016/j.chempr.2025.102433","url":null,"abstract":"<div><div>In this issue of <em>Chem</em>, Braunschweig et al. report the selective synthesis of an electron-precise tetra(amino)tetraborane featuring a puckered B<sub>4</sub> ring. Chemical redox reactions lead to the stable radical anion, dianion, and radical cation. The four charge states of the B<sub>4</sub> ring are poised to spark a revolution in boron chemistry.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102433"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143435641","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 : 2025-03-13DOI: 10.1016/j.chempr.2025.102485
Jason S. DesVeaux , Katrina M. Knauer
Plastic pollution is a pressing challenge, such that traditional recycling struggles to handle mixed waste. In the March issue of Chem Catalysis, Li et al. introduce a process that co-upcycles two societally important plastics, polyethylene terephthalate (PET) and polyoxymethylene (POM), offering a solution for more complex waste streams.
{"title":"Harnessing plastic depolymerization products to upcycle mixed waste into high-value chemicals","authors":"Jason S. DesVeaux , Katrina M. Knauer","doi":"10.1016/j.chempr.2025.102485","DOIUrl":"10.1016/j.chempr.2025.102485","url":null,"abstract":"<div><div>Plastic pollution is a pressing challenge, such that traditional recycling struggles to handle mixed waste. In the March issue of <em>Chem Catalysis</em>, Li et al. introduce a process that co-upcycles two societally important plastics, polyethylene terephthalate (PET) and polyoxymethylene (POM), offering a solution for more complex waste streams.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102485"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143463072","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}
Commodity chemical production is heavily dependent on fossil feedstocks. Transitioning to renewable resources is a pressing necessity, with green methanol being a promising candidate for rethinking chemical platforms. Here, we report how interlocking methanol-to-syngas reforming and hydroformylation of olefins may integrate methanol as a platform for accessing renewable oxo-products. This study demonstrates the importance of interlocking kinetics and selectivity of a ruthenium-catalyzed acceptorless dehydrogenation and a rhodium-catalyzed hydroformylation. Notably, coal- or natural gas-derived syngas can be substituted with fuel-grade e-methanol obtained from captured CO2 and green hydrogen. Although these conditions do not replicate large-scale industrial settings, we consider this dual-catalysis approach a proof of concept illustrating the potential to synthesize oxo-products entirely from CO2-derived methanol. We envision that redesigning chemical value chains to extend from renewable platforms like methanol could play a pivotal role toward establishing a more sustainable chemical industry.
{"title":"Integrating hydroformylations with methanol-to-syngas reforming","authors":"Andreas Bonde , Joakim Bøgelund Jakobsen , Alexander Ahrens , Weiheng Huang , Ralf Jackstell , Matthias Beller , Troels Skrydstrup","doi":"10.1016/j.chempr.2024.102396","DOIUrl":"10.1016/j.chempr.2024.102396","url":null,"abstract":"<div><div>Commodity chemical production is heavily dependent on fossil feedstocks. Transitioning to renewable resources is a pressing necessity, with green methanol being a promising candidate for rethinking chemical platforms. Here, we report how interlocking methanol-to-syngas reforming and hydroformylation of olefins may integrate methanol as a platform for accessing renewable oxo-products. This study demonstrates the importance of interlocking kinetics and selectivity of a ruthenium-catalyzed acceptorless dehydrogenation and a rhodium-catalyzed hydroformylation. Notably, coal- or natural gas-derived syngas can be substituted with fuel-grade e-methanol obtained from captured CO<sub>2</sub> and green hydrogen. Although these conditions do not replicate large-scale industrial settings, we consider this dual-catalysis approach a proof of concept illustrating the potential to synthesize oxo-products entirely from CO<sub>2</sub>-derived methanol. We envision that redesigning chemical value chains to extend from renewable platforms like methanol could play a pivotal role toward establishing a more sustainable chemical industry.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102396"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143083606","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 : 2025-03-13DOI: 10.1016/j.chempr.2024.10.013
Julie Yi-Hsuan Chen , Qing Shi , Xue Peng , Jean de Dieu Habimana , James Wang , William Sobolewski , Andy Hsien-Wei Yeh
We leverage AI-powered de novo protein design to create a new generation of luciferase catalysts, termed the neoLux series, which exhibit superior properties over native luciferases. These features include compact size, robust stability, cofactor independence, efficient cellular expression, higher catalytic efficiency, and unique substrate orthogonality, marking a significant advancement beyond the limitations of native luciferases. Additionally, we computationally designed highly efficient neoLux-fluorescent protein Förster resonance energy transfer (FRET) fusions capable of simultaneous multi-parametric imaging in cellulo and in vivo. Our pioneering approach has created a unified luminescent toolkit to allow for multi-colored tracking of cancer heterogeneity in vivo, paving the way for complex biological discovery.
{"title":"De novo luciferases enable multiplexed bioluminescence imaging","authors":"Julie Yi-Hsuan Chen , Qing Shi , Xue Peng , Jean de Dieu Habimana , James Wang , William Sobolewski , Andy Hsien-Wei Yeh","doi":"10.1016/j.chempr.2024.10.013","DOIUrl":"10.1016/j.chempr.2024.10.013","url":null,"abstract":"<div><div>We leverage AI-powered <em>de novo</em> protein design to create a new generation of luciferase catalysts, termed the neoLux series, which exhibit superior properties over native luciferases. These features include compact size, robust stability, cofactor independence, efficient cellular expression, higher catalytic efficiency, and unique substrate orthogonality, marking a significant advancement beyond the limitations of native luciferases. Additionally, we computationally designed highly efficient neoLux-fluorescent protein Förster resonance energy transfer (FRET) fusions capable of simultaneous multi-parametric imaging <em>in cellulo</em> and <em>in vivo</em>. Our pioneering approach has created a unified luminescent toolkit to allow for multi-colored tracking of cancer heterogeneity <em>in vivo</em>, paving the way for complex biological discovery.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102346"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599734","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 : 2025-03-13DOI: 10.1016/j.chempr.2024.10.029
Huai Qin Fu , Tingting Yu , Jessica White , Ji Wei Sun , Yuming Wu , Wen Jing Li , Nicholas M. Bedford , Yun Wang , Thomas E. Rufford , Cheng Lian , Porun Liu , Hua Gui Yang , Huijun Zhao
The path to practical production of targeted chemicals and fuels application via carbon dioxide reduction reactions (CO2RRs) remains a significant challenge mainly due to low CO2 solubility. Aiming to tackle this key issue, herein, we used the CuSbOx cathode-catalyzed reduction of CO2 to CO as a model system to quantitatively depict CO2 demand-supply and performance relationships. We propose a cathode/electrolyte interface model consisting of a porous catalyst layer, and we combined the experimental and computational COMSOL Multiphysics finite-element studies to quantitatively unveil CO2 demand-supply relationships and determine the maximum CO2 supply capacity in both stationary H cell and gas diffusion electrode (GDE) flow cell. This work exemplifies that experimentally measured catalytic performance may not accurately reflect the maximum capacity/intrinsic electrocatalytic activity of electrocatalysts and reveals that CO2 supply capacity in the GDE flow cell can be dramatically affected by the thickness of the liquid layer between the hydrophobic gas diffusion layer and the catalyst layer.
{"title":"Amorphous CuSbOx composite-catalyzed electrocatalytic reduction of CO2 to CO: CO2 demand-supply-regulated performance","authors":"Huai Qin Fu , Tingting Yu , Jessica White , Ji Wei Sun , Yuming Wu , Wen Jing Li , Nicholas M. Bedford , Yun Wang , Thomas E. Rufford , Cheng Lian , Porun Liu , Hua Gui Yang , Huijun Zhao","doi":"10.1016/j.chempr.2024.10.029","DOIUrl":"10.1016/j.chempr.2024.10.029","url":null,"abstract":"<div><div>The path to practical production of targeted chemicals and fuels application via carbon dioxide reduction reactions (CO<sub>2</sub>RRs) remains a significant challenge mainly due to low CO<sub>2</sub> solubility. Aiming to tackle this key issue, herein, we used the CuSbO<sub>x</sub> cathode-catalyzed reduction of CO<sub>2</sub> to CO as a model system to quantitatively depict CO<sub>2</sub> demand-supply and performance relationships. We propose a cathode/electrolyte interface model consisting of a porous catalyst layer, and we combined the experimental and computational COMSOL Multiphysics finite-element studies to quantitatively unveil CO<sub>2</sub> demand-supply relationships and determine the maximum CO<sub>2</sub> supply capacity in both stationary H cell and gas diffusion electrode (GDE) flow cell. This work exemplifies that experimentally measured catalytic performance may not accurately reflect the maximum capacity/intrinsic electrocatalytic activity of electrocatalysts and reveals that CO<sub>2</sub> supply capacity in the GDE flow cell can be dramatically affected by the thickness of the liquid layer between the hydrophobic gas diffusion layer and the catalyst layer.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102362"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142758663","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 : 2025-03-13DOI: 10.1016/j.chempr.2025.102495
Jian He , Chi-Ming Che
Using C–H substrates as limiting reagents to achieve non-directed C–H activation with high selectivity has been a long-standing challenge in organic synthesis. Recently in Nature Catalysis, Liu et al. introduce a biomimetic catalytic system that employs Cu(II)-bound tert-butoxy radicals for site-selective C–H abstraction, enabling highly efficient asymmetric C(sp3)–H oxidation.
{"title":"Manipulating alkoxy radicals for site- and enantioselective C–H oxidation","authors":"Jian He , Chi-Ming Che","doi":"10.1016/j.chempr.2025.102495","DOIUrl":"10.1016/j.chempr.2025.102495","url":null,"abstract":"<div><div>Using C–H substrates as limiting reagents to achieve non-directed C–H activation with high selectivity has been a long-standing challenge in organic synthesis. Recently in <em>Nature Catalysis</em>, Liu et al. introduce a biomimetic catalytic system that employs Cu(II)-bound <em>tert</em>-butoxy radicals for site-selective C–H abstraction, enabling highly efficient asymmetric C(sp<sup>3</sup>)–H oxidation.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102495"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608679","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 : 2025-03-13DOI: 10.1016/j.chempr.2025.102490
Fernando Fresno , Nicolas Keller
In this preview, we showcase Peters, Agapie, Atwater, and co-workers’ recent findings published in Device. The team developed a versatile and scalable selective-absorber-based photothermocatalytic reactor for sunlight-driven sustainable fuel synthesis. Ethylene oligomerization reactions using homogeneous and heterogeneous Ni catalysts were efficiently carried out in both batch and flow configurations.
{"title":"Versatile selective-absorber-based photothermocatalytic reactor for solar fuel synthesis","authors":"Fernando Fresno , Nicolas Keller","doi":"10.1016/j.chempr.2025.102490","DOIUrl":"10.1016/j.chempr.2025.102490","url":null,"abstract":"<div><div>In this preview, we showcase Peters, Agapie, Atwater, and co-workers’ recent findings published in <em>Device</em>. The team developed a versatile and scalable selective-absorber-based photothermocatalytic reactor for sunlight-driven sustainable fuel synthesis. Ethylene oligomerization reactions using homogeneous and heterogeneous Ni catalysts were efficiently carried out in both batch and flow configurations.</div></div>","PeriodicalId":268,"journal":{"name":"Chem","volume":"11 3","pages":"Article 102490"},"PeriodicalIF":19.1,"publicationDate":"2025-03-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143608690","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 : 2025-03-12DOI: 10.1016/j.chempr.2025.102481
Homan Kang, Seung Hun Park, Guliz Ersoy Ozmen, Won Hur, Jason Dinh, Haoran Wang, Vy Nguyen, Sung Ahn, Atsushi Yamashita, Wesley R. Stiles, Satoshi Kashiwagi, Kai Bao, Maged Henary, Hak Soo Choi
Early diagnosis is crucial for the effective treatment of rheumatoid arthritis because continuing inflammation can lead to irreversible joint damage. However, current diagnostic methods lack tissue-specific guidelines to monitor the progressive course of degenerative joint diseases. Here, we demonstrate that cartilage-targeting fluorophores (CARFs) exhibit a remarkable cartilage-specific affinity and offer advanced imaging capabilities in the near-infrared II (NIR-II) window, characterized by minimal tissue scattering and negligible autofluorescence. CARFs show little to no toxicity, both in vitro (up to 100 μM) and in vivo (3 μmol/kg via intravenous injection), suggesting clinical potential. Furthermore, CARFs in the NIR-II window enable the precise visualization of cartilage lining, serving as a reliable diagnostic indicator for the early detection of arthritis in preclinical mouse models. CARFs are NIR fluorescence-emitting targeted contrast agents for prognostic imaging of joint tissue, with the potential to revolutionize applications in tissue engineering, joint surgery, and drug development for inflammatory diseases.
{"title":"Cartilage-targeting fluorophores for early detection of arthritis in the NIR-II window","authors":"Homan Kang, Seung Hun Park, Guliz Ersoy Ozmen, Won Hur, Jason Dinh, Haoran Wang, Vy Nguyen, Sung Ahn, Atsushi Yamashita, Wesley R. Stiles, Satoshi Kashiwagi, Kai Bao, Maged Henary, Hak Soo Choi","doi":"10.1016/j.chempr.2025.102481","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102481","url":null,"abstract":"Early diagnosis is crucial for the effective treatment of rheumatoid arthritis because continuing inflammation can lead to irreversible joint damage. However, current diagnostic methods lack tissue-specific guidelines to monitor the progressive course of degenerative joint diseases. Here, we demonstrate that cartilage-targeting fluorophores (CARFs) exhibit a remarkable cartilage-specific affinity and offer advanced imaging capabilities in the near-infrared II (NIR-II) window, characterized by minimal tissue scattering and negligible autofluorescence. CARFs show little to no toxicity, both <em>in vitro</em> (up to 100 μM) and <em>in vivo</em> (3 μmol/kg via intravenous injection), suggesting clinical potential. Furthermore, CARFs in the NIR-II window enable the precise visualization of cartilage lining, serving as a reliable diagnostic indicator for the early detection of arthritis in preclinical mouse models. CARFs are NIR fluorescence-emitting targeted contrast agents for prognostic imaging of joint tissue, with the potential to revolutionize applications in tissue engineering, joint surgery, and drug development for inflammatory diseases.","PeriodicalId":268,"journal":{"name":"Chem","volume":"87 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143599571","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 : 2025-03-10DOI: 10.1016/j.chempr.2025.102489
Rui-Tian Ge, Feng Xiong, Zhen-Bang Chen, Yuanjie Wang, Lin Zheng, Jia Zhou, Di Wu, Shu-Yu Zhang
Indocyanine polymethines are among the most clinically promising probes for fluorescence imaging. Longer wavelength NIR-II probes offer enhanced fluorescence imaging performance by improving the tissue penetration depth and signal-to-noise ratio (SNR), but this often results in reduced brightness. Despite multiple attempts to redshift indocyanine polymethines' wavelengths, their emission wavelengths are restricted to 1,103 nm. We report the first indocyanine polymethines, Cy15s, emitting beyond 1,200 nm, with the longest maximum peak emission at 1,287 nm while maintaining a high brightness of 117.1 M−1⋅cm−1 in dichloroethane (DCM), 6-fold of the best performance of polymethine fluorophores emitting over 1,200 nm. The low cytotoxicity and remarkable optical properties enable high-quality near-infrared II (NIR-II)b angiography and long-term orthotopic tumor imaging. In addition to the relatively mature terminal groups research of polymethines, this study introduces a novel scaffold for conjugation chains, opening new avenues for the design and synthesis of NIR-II probes for deep-tissue imaging and tumor research.
{"title":"Indocyanine polymethine fluorophores with extended π-conjugation emitting beyond 1,200 nm for enhanced NIR-II imaging","authors":"Rui-Tian Ge, Feng Xiong, Zhen-Bang Chen, Yuanjie Wang, Lin Zheng, Jia Zhou, Di Wu, Shu-Yu Zhang","doi":"10.1016/j.chempr.2025.102489","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102489","url":null,"abstract":"Indocyanine polymethines are among the most clinically promising probes for fluorescence imaging. Longer wavelength NIR-II probes offer enhanced fluorescence imaging performance by improving the tissue penetration depth and signal-to-noise ratio (SNR), but this often results in reduced brightness. Despite multiple attempts to redshift indocyanine polymethines' wavelengths, their emission wavelengths are restricted to 1,103 nm. We report the first indocyanine polymethines, Cy15s, emitting beyond 1,200 nm, with the longest maximum peak emission at 1,287 nm while maintaining a high brightness of 117.1 M<sup>−1</sup>⋅cm<sup>−1</sup> in dichloroethane (DCM), 6-fold of the best performance of polymethine fluorophores emitting over 1,200 nm. The low cytotoxicity and remarkable optical properties enable high-quality near-infrared II (NIR-II)b angiography and long-term orthotopic tumor imaging. In addition to the relatively mature terminal groups research of polymethines, this study introduces a novel scaffold for conjugation chains, opening new avenues for the design and synthesis of NIR-II probes for deep-tissue imaging and tumor research.","PeriodicalId":268,"journal":{"name":"Chem","volume":"212 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143582569","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 : 2025-03-07DOI: 10.1016/j.chempr.2025.102462
Young Hyun Hong, Xiaofan Jia, Eleanor Stewart-Jones, Abhishek Kumar, Justin C. Wedal, Jose L. Alvarez-Hernandez, Carrie L. Donley, Albert Gang, Noah J. Gibson, Nilay Hazari, Madison Houck, Sungho Jeon, Jongbeom Kim, Hyeongjun Koh, James M. Mayer, Brandon Q. Mercado, Hannah S. Nedzbala, Nicole Piekut, Christine Quist, Eric Stach, Yihui Zhang
The reduction of carbon dioxide (CO2) to formate using molecular catalysts immobilized on high surface area porous silicon is described. Manganese complexes of the type (Rbpy)Mn(CO)3Br (bpy = 2,2′-bipyridine) were prepared with silatrane groups on the bpy ligand for attachment to oxide-coated porous silicon (SiOx-porSi). SiOx-porSi wafers were formed by heating hydrogen-terminated p-type porous silicon wafers under air, and the manganese complexes were immobilized on SiOx-porSi by heating at 80°C. The resulting hybrid photoelectrodes are photoelectrocatalysts for CO2 reduction in acetonitrile containing 2.0 M triethylamine and 2.0 M isopropanol, yielding formate with high selectivity (>96%) and current density (∼0.6 mA/cm2), excellent reproducibility, and a photovoltage of 280 mV at −1.75 V (versus ferrocenium/ferrocene) under 1 sun illumination. The applied potential is close to the equilibrium potential for CO2 reduction to formate. This work presents rare examples of immobilized molecular catalysts for CO2 reduction to formate and the first on semiconducting silicon.
{"title":"Photoelectrocatalytic reduction of CO2 to formate using immobilized molecular manganese catalysts on oxidized porous silicon","authors":"Young Hyun Hong, Xiaofan Jia, Eleanor Stewart-Jones, Abhishek Kumar, Justin C. Wedal, Jose L. Alvarez-Hernandez, Carrie L. Donley, Albert Gang, Noah J. Gibson, Nilay Hazari, Madison Houck, Sungho Jeon, Jongbeom Kim, Hyeongjun Koh, James M. Mayer, Brandon Q. Mercado, Hannah S. Nedzbala, Nicole Piekut, Christine Quist, Eric Stach, Yihui Zhang","doi":"10.1016/j.chempr.2025.102462","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102462","url":null,"abstract":"The reduction of carbon dioxide (CO<sub>2</sub>) to formate using molecular catalysts immobilized on high surface area porous silicon is described. Manganese complexes of the type (<sup>R</sup>bpy)Mn(CO)<sub>3</sub>Br (bpy = 2,2′-bipyridine) were prepared with silatrane groups on the bpy ligand for attachment to oxide-coated porous silicon (SiO<sub>x</sub>-porSi). SiO<sub>x</sub>-porSi wafers were formed by heating hydrogen-terminated p-type porous silicon wafers under air, and the manganese complexes were immobilized on SiO<sub>x</sub>-porSi by heating at 80°C. The resulting hybrid photoelectrodes are photoelectrocatalysts for CO<sub>2</sub> reduction in acetonitrile containing 2.0 M triethylamine and 2.0 M isopropanol, yielding formate with high selectivity (>96%) and current density (∼0.6 mA/cm<sup>2</sup>), excellent reproducibility, and a photovoltage of 280 mV at −1.75 V (versus ferrocenium/ferrocene) under 1 sun illumination. The applied potential is close to the equilibrium potential for CO<sub>2</sub> reduction to formate. This work presents rare examples of immobilized molecular catalysts for CO<sub>2</sub> reduction to formate and the first on semiconducting silicon.","PeriodicalId":268,"journal":{"name":"Chem","volume":"37 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569912","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号