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}
Pub Date : 2025-03-07DOI: 10.1016/j.chempr.2025.102480
Kelvin J.Y. Wu, Elena V. Aleksandrova, Paul J. Robinson, Amy E. Benedetto, Meiyi Yu, Ben I.C. Tresco, Dominic N.Y. See, Tong Jiang, Antonio Ramkissoon, Clémence F. Dunand, Maxim S. Svetlov, Joonho Lee, Yury S. Polikanov, Andrew G. Myers
We recently reported the conception and synthesis of cresomycin (CRM), a fully synthetic lincosamide antibiotic effective in vitro and in vivo against multidrug-resistant Gram-positive and Gram-negative bacteria. In this work, we describe the chemical synthesis and characterization of CRM sulfur atom replacement analogs C-CRM (S → CH2), O-CRM (S → O), and Se-CRM (S → Se). Comparison of high-resolution co-crystal structures showed that all four analogs adopted identical conformations when bound to the bacterial ribosome, but due to variations of ≤1 Å in the bond lengths between the anomeric carbon and the varied atoms, only the S and Se heteroatoms of CRM and Se-CRM, respectively, were positioned to interact with the π-face of nucleobase G2505. C-CRM and O-CRM did not benefit from such stabilizations, with correspondingly negative consequences in both target engagement and antibacterial activities. We therefore conclude that the sulfur atom of the lincosamides is important in ribosomal binding.
{"title":"Why sulfur is important in lincosamide antibiotics","authors":"Kelvin J.Y. Wu, Elena V. Aleksandrova, Paul J. Robinson, Amy E. Benedetto, Meiyi Yu, Ben I.C. Tresco, Dominic N.Y. See, Tong Jiang, Antonio Ramkissoon, Clémence F. Dunand, Maxim S. Svetlov, Joonho Lee, Yury S. Polikanov, Andrew G. Myers","doi":"10.1016/j.chempr.2025.102480","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102480","url":null,"abstract":"We recently reported the conception and synthesis of cresomycin (CRM), a fully synthetic lincosamide antibiotic effective <em>in vitro</em> and <em>in vivo</em> against multidrug-resistant Gram-positive and Gram-negative bacteria. In this work, we describe the chemical synthesis and characterization of CRM sulfur atom replacement analogs C-CRM (S → CH<sub>2</sub>), O-CRM (S → O), and Se-CRM (S → Se). Comparison of high-resolution co-crystal structures showed that all four analogs adopted identical conformations when bound to the bacterial ribosome, but due to variations of ≤1 Å in the bond lengths between the anomeric carbon and the varied atoms, only the S and Se heteroatoms of CRM and Se-CRM, respectively, were positioned to interact with the π-face of nucleobase G2505. C-CRM and O-CRM did not benefit from such stabilizations, with correspondingly negative consequences in both target engagement and antibacterial activities. We therefore conclude that the sulfur atom of the lincosamides is important in ribosomal binding.","PeriodicalId":268,"journal":{"name":"Chem","volume":"195 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569907","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.2025.102456
Andrew W. Heard, Samuel E. Clark, Charlie T. McTernan, Tanya K. Ronson, Petr Rozhin, Barbara Rossi, Silvia Marchesan, Jonathan R. Nitschke
Here, we report two (AgI3I)4L4 metal-organic cages that each contain a previously unobserved trisilver(I) iodide cluster at their vertices. Clusters containing fewer than 10 AgI ions are challenging to synthesize in an atomically precise manner. Previous work has demonstrated the potential of the approach of generating such clusters during the formation of higher-order metal-organic cage superstructures, but too few examples were known for design principles to be deciphered. Through analysis of the set of such cages reported herein and previously, we elaborate a set of design principles for their synthesis.
{"title":"Two (AgI3I)4L4 cages elucidate the rules for silver-cluster vertex design","authors":"Andrew W. Heard, Samuel E. Clark, Charlie T. McTernan, Tanya K. Ronson, Petr Rozhin, Barbara Rossi, Silvia Marchesan, Jonathan R. Nitschke","doi":"10.1016/j.chempr.2025.102456","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102456","url":null,"abstract":"Here, we report two (Ag<sup>I</sup><sub>3</sub>I)<sub>4</sub>L<sub>4</sub> metal-organic cages that each contain a previously unobserved trisilver(I) iodide cluster at their vertices. Clusters containing fewer than 10 Ag<sup>I</sup> ions are challenging to synthesize in an atomically precise manner. Previous work has demonstrated the potential of the approach of generating such clusters during the formation of higher-order metal-organic cage superstructures, but too few examples were known for design principles to be deciphered. Through analysis of the set of such cages reported herein and previously, we elaborate a set of design principles for their synthesis.","PeriodicalId":268,"journal":{"name":"Chem","volume":"15 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143569911","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 : 2025-03-06DOI: 10.1016/j.chempr.2025.102487
Hoai T.B. Pham, Xiaoyu Fang, Ji Yong Choi, Shaofeng Huang, Jihye Park
Integrating metallic charge transport with high porosity in a single material can unlock significant advancements in energy storage, electrocatalysis, and chemiresistive sensing. However, these properties rarely coexist due to the conflicting need for a high charge carrier density and the presence of voids. Herein, we report a new macrocyclic ligand, 2,3,8,9,14,15-hexaaminotribenzocyclyne (HATC) and its electrically conductive metal-organic framework (EC-MOF), coordinated with nickel nodes to render Ni-HATC as nanoporous synthetic metal. HATC provides intrinsic pockets for extra porosity, while its six amino and three alkyne groups significantly enhance electron density for realizing metallic behaviors in Ni-HATC. Consequently, Ni-HATC achieves exceptional conductivities of 20 S/cm in thin films and 3 S/cm in bulk, with a high surface area of 1,000 m2/g. Our findings showcase a unique material combining metallic charge transport and high porosity, opening new possibilities for future synthetically nanoporous metallic materials.
{"title":"Nanoporous synthetic metal: A nickel MOF with an amino-functionalized macrocyclic ligand","authors":"Hoai T.B. Pham, Xiaoyu Fang, Ji Yong Choi, Shaofeng Huang, Jihye Park","doi":"10.1016/j.chempr.2025.102487","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102487","url":null,"abstract":"Integrating metallic charge transport with high porosity in a single material can unlock significant advancements in energy storage, electrocatalysis, and chemiresistive sensing. However, these properties rarely coexist due to the conflicting need for a high charge carrier density and the presence of voids. Herein, we report a new macrocyclic ligand, 2,3,8,9,14,15-hexaaminotribenzocyclyne (HATC) and its electrically conductive metal-organic framework (EC-MOF), coordinated with nickel nodes to render Ni-HATC as nanoporous synthetic metal. HATC provides intrinsic pockets for extra porosity, while its six amino and three alkyne groups significantly enhance electron density for realizing metallic behaviors in Ni-HATC. Consequently, Ni-HATC achieves exceptional conductivities of 20 S/cm in thin films and 3 S/cm in bulk, with a high surface area of 1,000 m<sup>2</sup>/g. Our findings showcase a unique material combining metallic charge transport and high porosity, opening new possibilities for future synthetically nanoporous metallic materials.","PeriodicalId":268,"journal":{"name":"Chem","volume":"16 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561044","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 : 2025-03-06DOI: 10.1016/j.chempr.2025.102488
Wang Wang, Bodi Zhao, Xiaotian Qi, M. Kevin Brown
Tetrahydroisoquinolines (THIQ) are prevalent scaffolds found in natural products and pharmaceutical agents. Therefore, new methods for the synthesis of this motif, especially with unique stereochemistry or substitution patterns, are highly desirable. Herein, a new disconnection is demonstrated that combines sulfonylimines and alkenes. The convergent process operates by photoinduced energy transfer. High selectivities for the formation of the anti-isomer were observed. In addition, through the use of highly substituted alkenes, the synthesis of quaternary carbon containing tetrahydroisoquinolines can be achieved. Finally, mechanistic studies are included, revealing that the high selectivity observed is due to subtle variation of the highest occupied molecular orbital (HOMO) energies.
{"title":"An unconventional photochemical tetrahydroisoquinoline synthesis from sulfonylimines and alkenes","authors":"Wang Wang, Bodi Zhao, Xiaotian Qi, M. Kevin Brown","doi":"10.1016/j.chempr.2025.102488","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102488","url":null,"abstract":"Tetrahydroisoquinolines (THIQ) are prevalent scaffolds found in natural products and pharmaceutical agents. Therefore, new methods for the synthesis of this motif, especially with unique stereochemistry or substitution patterns, are highly desirable. Herein, a new disconnection is demonstrated that combines sulfonylimines and alkenes. The convergent process operates by photoinduced energy transfer. High selectivities for the formation of the anti-isomer were observed. In addition, through the use of highly substituted alkenes, the synthesis of quaternary carbon containing tetrahydroisoquinolines can be achieved. Finally, mechanistic studies are included, revealing that the high selectivity observed is due to subtle variation of the highest occupied molecular orbital (HOMO) energies.","PeriodicalId":268,"journal":{"name":"Chem","volume":"12 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561043","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 : 2025-03-05DOI: 10.1016/j.chempr.2025.102461
Hyewon Yun, Suhwan Yoo, Jihoon Son, Jae Hyung Kim, Jingwen Wu, Kun Jiang, Hyeyoung Shin, Yun Jeong Hwang
Understanding the intricacies of electron and proton transfer steps is imperative to exploiting the CO2 reduction reaction (CO2RR). Here, we highlight the significance of proton transfer by demonstrating that switching the proton supplier from H2O to H3O+ in a strongly acidic electrolyte (pH < 2) accelerates CO2RR kinetics and allows Ni–N–C to achieve higher CO activities. Conversely, under mildly acidic conditions, CO production rate remains similar even with concentrated K+. Operando infrared spectroscopy supports pH-dependent changes in interfacial water structures, and density function theory simulations reveal a synergistic effect of cations and H3O+ to stabilize intermediates. Ni–N–C, exhibiting a large overpotential for hydrogen evolution, promotes CO2RR with prominent ∗CO adsorption at pH 1.7 under higher cation concentrations. Its membrane electrode assembly (MEA) system achieves 95% CO2 conversion efficiency and high CO selectivity for 50 h by optimizing proton and cation transport. This study presents opportunities to accelerate CO2RR in acidic environments by H3O+.
{"title":"Strong cation concentration effect of Ni–N–C electrocatalysts in accelerating acidic CO2 reduction reaction","authors":"Hyewon Yun, Suhwan Yoo, Jihoon Son, Jae Hyung Kim, Jingwen Wu, Kun Jiang, Hyeyoung Shin, Yun Jeong Hwang","doi":"10.1016/j.chempr.2025.102461","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102461","url":null,"abstract":"Understanding the intricacies of electron and proton transfer steps is imperative to exploiting the CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR). Here, we highlight the significance of proton transfer by demonstrating that switching the proton supplier from H<sub>2</sub>O to H<sub>3</sub>O<sup>+</sup> in a strongly acidic electrolyte (pH < 2) accelerates CO<sub>2</sub>RR kinetics and allows Ni–N–C to achieve higher CO activities. Conversely, under mildly acidic conditions, CO production rate remains similar even with concentrated K<sup>+</sup>. <em>Operando</em> infrared spectroscopy supports pH-dependent changes in interfacial water structures, and density function theory simulations reveal a synergistic effect of cations and H<sub>3</sub>O<sup>+</sup> to stabilize intermediates. Ni–N–C, exhibiting a large overpotential for hydrogen evolution, promotes CO<sub>2</sub>RR with prominent <sup>∗</sup>CO adsorption at pH 1.7 under higher cation concentrations. Its membrane electrode assembly (MEA) system achieves 95% CO<sub>2</sub> conversion efficiency and high CO selectivity for 50 h by optimizing proton and cation transport. This study presents opportunities to accelerate CO<sub>2</sub>RR in acidic environments by H<sub>3</sub>O<sup>+</sup>.","PeriodicalId":268,"journal":{"name":"Chem","volume":"4 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143547068","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 : 2025-03-05DOI: 10.1016/j.chempr.2025.102479
Zhi Yuan Lee, Sirin Kamarulzaman, Rizqullah Rasyiddin, Sheila Y.X. Sim, Georgina E.K.K. Seah, Ai Wei Gan, Zibiao Li, Zhuang Mao Png, Shermin S. Goh
Covalent adaptable networks (CANs) are polymers crosslinked via dynamic covalent bonds (DCBs), endowing the networks with both thermoset-like stability and thermoplastic-like recyclability. Although post-polymerization crosslinking of thermoplastics is an efficient strategy to form CANs, the process is non-trivial, especially for poly(olefins) that have low functionality and a fully hydrocarbon backbone. Herein, we introduce perflurophenyl azide-based nitrene crosslinkers to install disulfide, imine, and acetal DCBs into poly(olefins) and other thermoplastics, thereby converting them into CANs. Crosslinking was effective for a wide range of thermoplastics, imparting both dimensional and solvent stability. The resultant CANs could also exhibit enhanced mechanical performance, such as doubling of tensile toughness and self-healing ability. Unlike traditional thermosets, the DCBs enabled these CANs to be chemically and/or mechanically recycled multiple times. This methodology has the advantage of utilizing existing and even post-consumer plastic blends as starting materials, improving their thermo-mechanical properties while maintaining recyclability of the synthesized CANs.
{"title":"Dynamic crosslinking of thermoplastics via perfluorophenyl nitrene C–H insertion to form recyclable thermosets","authors":"Zhi Yuan Lee, Sirin Kamarulzaman, Rizqullah Rasyiddin, Sheila Y.X. Sim, Georgina E.K.K. Seah, Ai Wei Gan, Zibiao Li, Zhuang Mao Png, Shermin S. Goh","doi":"10.1016/j.chempr.2025.102479","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102479","url":null,"abstract":"Covalent adaptable networks (CANs) are polymers crosslinked via dynamic covalent bonds (DCBs), endowing the networks with both thermoset-like stability and thermoplastic-like recyclability. Although post-polymerization crosslinking of thermoplastics is an efficient strategy to form CANs, the process is non-trivial, especially for poly(olefins) that have low functionality and a fully hydrocarbon backbone. Herein, we introduce perflurophenyl azide-based nitrene crosslinkers to install disulfide, imine, and acetal DCBs into poly(olefins) and other thermoplastics, thereby converting them into CANs. Crosslinking was effective for a wide range of thermoplastics, imparting both dimensional and solvent stability. The resultant CANs could also exhibit enhanced mechanical performance, such as doubling of tensile toughness and self-healing ability. Unlike traditional thermosets, the DCBs enabled these CANs to be chemically and/or mechanically recycled multiple times. This methodology has the advantage of utilizing existing and even post-consumer plastic blends as starting materials, improving their thermo-mechanical properties while maintaining recyclability of the synthesized CANs.","PeriodicalId":268,"journal":{"name":"Chem","volume":"30 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546621","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 : 2025-03-05DOI: 10.1016/j.chempr.2024.102391
Qiong Liu, Hui Cheng, Ching Kit Tommy Wun, Tianxiang Chen, Tsz Woon Benedict Lo, Fuxian Wang
Photocatalytic reduction of CO2 in flue gas faces significant challenges due to the low CO2 concentration and the presence of oxygen (O2), which induces competitive oxygen reduction reactions, as well as the sluggish kinetics and complex product separation of oxidation half-reactions. Herein, we developed a dual copper (Cu)/platinum (Pt) atom on carbon nitride (CN-CuPt) photocatalyst, achieving synergistic ethylene production through low CO2 concentration (i.e., 12% CO2) reduction coupled with isopropanol oxidation to acetone for the first example. A benchmark photocatalytic ethylene yield of 778.6 μmolh−1gcat−1 with a high selectivity of 87.0% is obtained, outperforming all the state-of-the-art CO2 photocatalysts. What’s more, the CN-CuPt exhibits high oxygen tolerance, and more than 90% of its performance is retained under the interference of 5% oxygen due to oxygen inhibition by Cu species. Our strategy of regulating adsorption sites shows great potential for designing catalysts for practical photocatalytic reduction of flue gas.
{"title":"Oxygen-tolerant photocatalytic conversion of simulated flue gas to ethylene","authors":"Qiong Liu, Hui Cheng, Ching Kit Tommy Wun, Tianxiang Chen, Tsz Woon Benedict Lo, Fuxian Wang","doi":"10.1016/j.chempr.2024.102391","DOIUrl":"https://doi.org/10.1016/j.chempr.2024.102391","url":null,"abstract":"Photocatalytic reduction of CO<sub>2</sub> in flue gas faces significant challenges due to the low CO<sub>2</sub> concentration and the presence of oxygen (O<sub>2</sub>), which induces competitive oxygen reduction reactions, as well as the sluggish kinetics and complex product separation of oxidation half-reactions. Herein, we developed a dual copper (Cu)/platinum (Pt) atom on carbon nitride (CN-CuPt) photocatalyst, achieving synergistic ethylene production through low CO<sub>2</sub> concentration (i.e., 12% CO<sub>2</sub>) reduction coupled with isopropanol oxidation to acetone for the first example. A benchmark photocatalytic ethylene yield of 778.6 μmolh<sup>−1</sup>g<sub>cat</sub><sup>−1</sup> with a high selectivity of 87.0% is obtained, outperforming all the state-of-the-art CO<sub>2</sub> photocatalysts. What’s more, the CN-CuPt exhibits high oxygen tolerance, and more than 90% of its performance is retained under the interference of 5% oxygen due to oxygen inhibition by Cu species. Our strategy of regulating adsorption sites shows great potential for designing catalysts for practical photocatalytic reduction of flue gas.","PeriodicalId":268,"journal":{"name":"Chem","volume":"67 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143561047","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 : 2025-03-05DOI: 10.1016/j.chempr.2025.102460
Amrita Singh-Morgan, Kim Trösch, Anna Weinfurter, Michael Inniger, Yuan-Zi Xu, Victor Mougel
The electrochemical synthesis of ammonia presents a promising pathway to decarbonize and electrify the production of the world’s second-largest commodity chemical. Among potential reactants, NOx gases stand out owing to their favorable thermodynamics, advantageous kinetics, and availability from both combustion emissions and nitrogen-fixation processes, such as plasma-induced atmospheric nitrogen oxidation. However, the typically low concentration of NOx in these sources poses significant challenges for electrochemical performance, particularly due to limitations in reactant mass transport. In this work, we report on the use of a porous nickel catalyst in a membrane electrode assembly (MEA) electrolyzer to enable the direct use of a dilute nitric oxide (NO) feed. The rational optimization of reactant mass transport led to the attainment of maximum values of NO-to-NH3 single-pass conversion of 93%, faradaic efficiency for ammonia of 92%, and ammonium production rate of 556 μmol/h⋅cm2.
{"title":"Efficient electrochemical conversion of nitric oxide to ammonia using a porous nickel catalyst in a membrane electrode assembly electrolyzer","authors":"Amrita Singh-Morgan, Kim Trösch, Anna Weinfurter, Michael Inniger, Yuan-Zi Xu, Victor Mougel","doi":"10.1016/j.chempr.2025.102460","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102460","url":null,"abstract":"The electrochemical synthesis of ammonia presents a promising pathway to decarbonize and electrify the production of the world’s second-largest commodity chemical. Among potential reactants, NO<sub>x</sub> gases stand out owing to their favorable thermodynamics, advantageous kinetics, and availability from both combustion emissions and nitrogen-fixation processes, such as plasma-induced atmospheric nitrogen oxidation. However, the typically low concentration of NO<sub>x</sub> in these sources poses significant challenges for electrochemical performance, particularly due to limitations in reactant mass transport. In this work, we report on the use of a porous nickel catalyst in a membrane electrode assembly (MEA) electrolyzer to enable the direct use of a dilute nitric oxide (NO) feed. The rational optimization of reactant mass transport led to the attainment of maximum values of NO-to-NH<sub>3</sub> single-pass conversion of 93%, faradaic efficiency for ammonia of 92%, and ammonium production rate of 556 μmol/h⋅cm<sup>2</sup>.","PeriodicalId":268,"journal":{"name":"Chem","volume":"67 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143546620","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}
Ammonia (NH3) is considered a biomarker of liver and kidney diseases; sensitive and visible fluorescence sensors are expected to achieve quantitative detection of breath NH3, although low accuracy makes them difficult to apply in breath tests. Herein, we adopted a “double-response-reverse fluorescence” strategy via in situ encapsulation of a metal nanocluster (MNC) into a hydrogen-bonded organic framework, successfully constructing an ultra-accurate ratiometric fluorescence sensor (Pt2Cu4@HOF-101). With a combination of π-conjugated HOF and luminescent MNC, two kinds of NH3 recognition sites were preciously assembled and raised significant orbital energy changes, thus realizing a strong response to trace NH3. The precision-assembled Pt2Cu4@HOF-101 has been eloquently inspected by three-dimensional electron diffraction, which comprehensively uncovered the structure-induced double-response-reverse sensing mechanism. Notably, Pt2Cu4@HOF-101 enabled exact quantification of the NH3 exhaled, and the measured expiratory concentration was highly positively correlated with the blood test, which offers a new approach for the painless diagnosis of liver and kidney diseases.
{"title":"Encapsulation of metal nanoclusters into hydrogen-bonded organic frameworks for double-response-reverse ammonia fluorescence sensing","authors":"Yuxin Wang, Jia Yao, Shitao Wu, Chao Zhi, Lifei Yin, Zhengxuan Song, Jing Wang, Lixia Ling, Yanhang Ma, Daliang Zhang, Jinping Li, Libo Li, Banglin Chen","doi":"10.1016/j.chempr.2025.102457","DOIUrl":"https://doi.org/10.1016/j.chempr.2025.102457","url":null,"abstract":"Ammonia (NH<sub>3</sub>) is considered a biomarker of liver and kidney diseases; sensitive and visible fluorescence sensors are expected to achieve quantitative detection of breath NH<sub>3</sub>, although low accuracy makes them difficult to apply in breath tests. Herein, we adopted a “double-response-reverse fluorescence” strategy via <em>in situ</em> encapsulation of a metal nanocluster (MNC) into a hydrogen-bonded organic framework, successfully constructing an ultra-accurate ratiometric fluorescence sensor (Pt<sub>2</sub>Cu<sub>4</sub>@HOF-101). With a combination of π-conjugated HOF and luminescent MNC, two kinds of NH<sub>3</sub> recognition sites were preciously assembled and raised significant orbital energy changes, thus realizing a strong response to trace NH<sub>3</sub>. The precision-assembled Pt<sub>2</sub>Cu<sub>4</sub>@HOF-101 has been eloquently inspected by three-dimensional electron diffraction, which comprehensively uncovered the structure-induced double-response-reverse sensing mechanism. Notably, Pt<sub>2</sub>Cu<sub>4</sub>@HOF-101 enabled exact quantification of the NH<sub>3</sub> exhaled, and the measured expiratory concentration was highly positively correlated with the blood test, which offers a new approach for the painless diagnosis of liver and kidney diseases.","PeriodicalId":268,"journal":{"name":"Chem","volume":"35 1","pages":""},"PeriodicalIF":23.5,"publicationDate":"2025-03-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143539184","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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