Extensive research has been conducted on chiral porphyrin-metal complex (M = Co, Rh, Ru, Fe)-catalyzed asymmetric cyclopropanation of alkenes. However, the corresponding iridium complex has scarcely been exploited for this purpose. We report herein that the reaction of 2,2,2-trichloroethyl (TCE) α-aryldiazoacetates 1 with alkenes 2 in the presence of a catalytic amount of [Ir(Por∗)(CO)Cl] (1.0 mol %) yields a single diastereomer of 1,1,2-trisubstituted cyclopropanes in high yields with excellent enantioselectivities. A β-axially chiral porphyrin, developed recently in our laboratory, serves as an efficient supporting ligand.
{"title":"Highly diastereoselective and enantioselective cyclopropanation of alkenes catalyzed by a chiral iridium(III) porphyrin complex","authors":"Sheng-Yu Li, Shanshan Yuan, Xiao-Ming Zhao, Qunlong Wang, Jieping Zhu, Sheng-Cai Zheng","doi":"10.1016/j.checat.2024.101262","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101262","url":null,"abstract":"Extensive research has been conducted on chiral porphyrin-metal complex (M = Co, Rh, Ru, Fe)-catalyzed asymmetric cyclopropanation of alkenes. However, the corresponding iridium complex has scarcely been exploited for this purpose. We report herein that the reaction of 2,2,2-trichloroethyl (TCE) α-aryldiazoacetates <strong>1</strong> with alkenes <strong>2</strong> in the presence of a catalytic amount of [Ir(Por∗)(CO)Cl] (1.0 mol %) yields a single diastereomer of 1,1,2-trisubstituted cyclopropanes in high yields with excellent enantioselectivities. A β-axially chiral porphyrin, developed recently in our laboratory, serves as an efficient supporting ligand.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"128 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385275","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-11DOI: 10.1016/j.checat.2025.101263
Jialu Li, Jinqi Xiong, Minghao Sun, Fengwang Li
Carbon dioxide (CO2) electrocarboxylation presents a promising solution for converting harmful emissions into valuable products, which aligns with the broader goal of establishing a sustainable, carbon-neutral economy. The field has seen significant progress in the electrochemical synthesis of carboxylic acids and related compounds, which are widely used in the pharmaceutical and chemical industries. This review emphasizes the primary obstacles hindering the practical application of electrocarboxylation, most notably the reliance on sacrificial anodes and the inefficiencies associated with traditional reactor designs. It provides a discussion of recent progress and innovative strategies aimed at overcoming these barriers. Specifically, the review examines sacrificial-anode methods and the challenges they pose, such as the need for frequent replenishment and issues with cathode passivation. It also explores strategies for avoiding anode consumption, which include using electrolytes or additives as sacrificial agents and employing paired electrolysis. Furthermore, the potential of microfluidic reactors in enhancing the efficiency of CO2 electrocarboxylation is highlighted, given their capacity to offer precise control over reaction conditions. The review concludes with a perspective on the future of the field by identifying areas that are ripe for additional research and development to ensure the industrial viability of CO2 electrocarboxylation.
{"title":"Anodic reactions matter for cathodic electrocarboxylation with CO2","authors":"Jialu Li, Jinqi Xiong, Minghao Sun, Fengwang Li","doi":"10.1016/j.checat.2025.101263","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101263","url":null,"abstract":"Carbon dioxide (CO<sub>2</sub>) electrocarboxylation presents a promising solution for converting harmful emissions into valuable products, which aligns with the broader goal of establishing a sustainable, carbon-neutral economy. The field has seen significant progress in the electrochemical synthesis of carboxylic acids and related compounds, which are widely used in the pharmaceutical and chemical industries. This review emphasizes the primary obstacles hindering the practical application of electrocarboxylation, most notably the reliance on sacrificial anodes and the inefficiencies associated with traditional reactor designs. It provides a discussion of recent progress and innovative strategies aimed at overcoming these barriers. Specifically, the review examines sacrificial-anode methods and the challenges they pose, such as the need for frequent replenishment and issues with cathode passivation. It also explores strategies for avoiding anode consumption, which include using electrolytes or additives as sacrificial agents and employing paired electrolysis. Furthermore, the potential of microfluidic reactors in enhancing the efficiency of CO<sub>2</sub> electrocarboxylation is highlighted, given their capacity to offer precise control over reaction conditions. The review concludes with a perspective on the future of the field by identifying areas that are ripe for additional research and development to ensure the industrial viability of CO<sub>2</sub> electrocarboxylation.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"87 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385276","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-10DOI: 10.1016/j.checat.2024.101259
Bin Zhu, Jie Yang, Qiuge Wang, Xiao Yu, Shilin Fan, Weiping Xie, Jian Zhang, Chunlin Chen
The intersection of corrosion engineering for constructing high-performance electrocatalysts and the efficient upgrading of biomass represents two vibrant, sustainable research themes that promise exciting outcomes when combined. In this study, we achieve the highly selective hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) over corrosion-induced CoCu microwire arrays on copper foam (CoCuMW/CF). An HMF conversion of 95.7% and a BHMF yield of 85.4% can be achieved in the electrochemical process. Mechanistic investigations indicate that the reaction pathway is primarily governed by the Langmuir-Hinshelwood (L-H) mechanism. Density functional theory (DFT) calculations reveal that the CoCu interface exhibits lower free energy barriers for the hydrogenation steps of HMF, which significantly enhances the catalytic performance and BHMF selectivity. The induction of corrosion enhances the electrochemical hydrogenation performance of the copper-based electrocatalyst, which holds significant value in reducing catalyst costs and accelerating the application of HMF electrohydrogenation.
{"title":"Corrosion-induced CoCu microwire arrays for efficient electroreduction of 5-hydroxymethylfurfural","authors":"Bin Zhu, Jie Yang, Qiuge Wang, Xiao Yu, Shilin Fan, Weiping Xie, Jian Zhang, Chunlin Chen","doi":"10.1016/j.checat.2024.101259","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101259","url":null,"abstract":"The intersection of corrosion engineering for constructing high-performance electrocatalysts and the efficient upgrading of biomass represents two vibrant, sustainable research themes that promise exciting outcomes when combined. In this study, we achieve the highly selective hydrogenation of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) over corrosion-induced CoCu microwire arrays on copper foam (CoCuMW/CF). An HMF conversion of 95.7% and a BHMF yield of 85.4% can be achieved in the electrochemical process. Mechanistic investigations indicate that the reaction pathway is primarily governed by the Langmuir-Hinshelwood (L-H) mechanism. Density functional theory (DFT) calculations reveal that the CoCu interface exhibits lower free energy barriers for the hydrogenation steps of HMF, which significantly enhances the catalytic performance and BHMF selectivity. The induction of corrosion enhances the electrochemical hydrogenation performance of the copper-based electrocatalyst, which holds significant value in reducing catalyst costs and accelerating the application of HMF electrohydrogenation.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"12 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375286","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-07DOI: 10.1016/j.checat.2024.101260
Jie Fu, Shuhua Chen, Xinlin Liu, Haoyue Yang, Yeping Xie, Qiao Zhang, Jinxing Chen, Muhan Cao
Photocatalytic hydrogen peroxide (H2O2) production is a promising green technology, but it typically relies on costly sacrificial agents to enhance charge separation and catalytic efficiency. Waste polymers offer a cost-effective alternative, effectively addressing waste management and resource utilization challenges. Herein, we employ waste polymer polyvinyl alcohol (PVA) as a sacrificial agent for photocatalytic H2O2 production, avoiding the harsh and complex hydrolysis process of polyesters and polyolefins. Importantly, the unique structure of PVA creates a localized microenvironment with abundant hydroxyl groups, significantly increasing the H2O2 yield compared with those of conventional sacrificial agents. Additionally, the introduction of iron ions triggers a photo-self-Fenton (PSF) reaction. The hydroxyl groups on the PVA chain facilitate strong interactions with iron species, thereby enhancing the Fe3+/Fe2+ redox cycle and enabling the simultaneous removal of both PVA and other pollutants. This approach offers a novel and sustainable pathway for the direct utilization of polymer waste.
{"title":"Soluble polymer microenvironments promote photocatalytic hydrogen peroxide production and self-Fenton reactions","authors":"Jie Fu, Shuhua Chen, Xinlin Liu, Haoyue Yang, Yeping Xie, Qiao Zhang, Jinxing Chen, Muhan Cao","doi":"10.1016/j.checat.2024.101260","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101260","url":null,"abstract":"Photocatalytic hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) production is a promising green technology, but it typically relies on costly sacrificial agents to enhance charge separation and catalytic efficiency. Waste polymers offer a cost-effective alternative, effectively addressing waste management and resource utilization challenges. Herein, we employ waste polymer polyvinyl alcohol (PVA) as a sacrificial agent for photocatalytic H<sub>2</sub>O<sub>2</sub> production, avoiding the harsh and complex hydrolysis process of polyesters and polyolefins. Importantly, the unique structure of PVA creates a localized microenvironment with abundant hydroxyl groups, significantly increasing the H<sub>2</sub>O<sub>2</sub> yield compared with those of conventional sacrificial agents. Additionally, the introduction of iron ions triggers a photo-self-Fenton (PSF) reaction. The hydroxyl groups on the PVA chain facilitate strong interactions with iron species, thereby enhancing the Fe<sup>3+</sup>/Fe<sup>2+</sup> redox cycle and enabling the simultaneous removal of both PVA and other pollutants. This approach offers a novel and sustainable pathway for the direct utilization of polymer waste.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"36 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258620","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-07DOI: 10.1016/j.checat.2024.101261
Li-Qin She, Dao-Ming Wang, Yichen Wu, Peng Wang
An alcohol-directed 1,2-dicarbofunctionalization of alkenyl alcohols has been realized with aryl/alkenyl boronic acids and alkyl halides as the coupling partners. This reaction was enabled by a commercially available bulky 3-amyl β-diketone (Amacac) ligand, which enhances the reactivity and suppresses many competitive processes. With alcohol as a weak native directing group, this protocol delivers 1,2-arylalkylated and 1,2-alkenylalkylated alcohols with high efficiency, high regioselectivities, a broad substrate scope, and exceptional functional group tolerance. Notably, this methodology facilitates the modular synthesis of biologically active compounds and key alcohol-containing synthetic intermediates. Preliminary mechanistic studies shed light on the neutral coordination of alcohol functionality to nickel catalysts and the origin of regioselectivity.
{"title":"Ligand-enabled, Ni-catalyzed dicarbofunctionalization of alkenyl alcohols","authors":"Li-Qin She, Dao-Ming Wang, Yichen Wu, Peng Wang","doi":"10.1016/j.checat.2024.101261","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101261","url":null,"abstract":"An alcohol-directed 1,2-dicarbofunctionalization of alkenyl alcohols has been realized with aryl/alkenyl boronic acids and alkyl halides as the coupling partners. This reaction was enabled by a commercially available bulky 3-amyl β-diketone (Amacac) ligand, which enhances the reactivity and suppresses many competitive processes. With alcohol as a weak native directing group, this protocol delivers 1,2-arylalkylated and 1,2-alkenylalkylated alcohols with high efficiency, high regioselectivities, a broad substrate scope, and exceptional functional group tolerance. Notably, this methodology facilitates the modular synthesis of biologically active compounds and key alcohol-containing synthetic intermediates. Preliminary mechanistic studies shed light on the neutral coordination of alcohol functionality to nickel catalysts and the origin of regioselectivity.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"47 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143258733","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-06DOI: 10.1016/j.checat.2024.101257
Haifeng Chen, Cai Zhai, Chen Zhu, Magnus Rueping
Organogermanes have played a significant role in organic chemistry, and effective strategies for accessing various organogermanes are crucial for advancing their applications. However, the formation of allylgermanes under electrophile coupling is still unexplored. Herein, we describe a germylative allylation applying readily accessible allylic carbonates and chlorogermanes. The newly developed method demonstrates good selectivity and high functional group compatibility under mild conditions and provides a variety of allylgermanes, as well as allyl tin, in good yields. Mechanistic and density functional theory (DFT) studies revealed the synergistic catalytic process in detail.
{"title":"Allylgermane synthesis via facile and general nickela-electrocatalyzed electrophile coupling","authors":"Haifeng Chen, Cai Zhai, Chen Zhu, Magnus Rueping","doi":"10.1016/j.checat.2024.101257","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101257","url":null,"abstract":"Organogermanes have played a significant role in organic chemistry, and effective strategies for accessing various organogermanes are crucial for advancing their applications. However, the formation of allylgermanes under electrophile coupling is still unexplored. Herein, we describe a germylative allylation applying readily accessible allylic carbonates and chlorogermanes. The newly developed method demonstrates good selectivity and high functional group compatibility under mild conditions and provides a variety of allylgermanes, as well as allyl tin, in good yields. Mechanistic and density functional theory (DFT) studies revealed the synergistic catalytic process in detail.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"55 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192392","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-02-06DOI: 10.1016/j.checat.2024.101258
Kaustubh J. Sawant, Junxian Gao, Jeffrey T. Miller, Zhenhua Zeng, Dmitry Zemlyanov, Jeffrey P. Greeley
In this study, we explore how the formation of self-assembled porous hydroxylated phases provides a strategy to modulate surface chemistry while preserving the number of active sites. Specifically, we investigated graphene-like ZnO films and related Zn6O5H5 overlayers on Pt(111) as model inverse catalysts with relevance to industrial catalysis. By combining surface science experiments and density functional theory (DFT) calculations, we demonstrate that the formation of ZnO films minimally affects the adsorption properties of CO, a common probe adsorbate for industrially relevant reactions, while significantly blocking surface Pt sites. By contrast, the porous Zn6O5H5 films on Pt not only modulate CO adsorption energies and site preferences, mediated by charge donation and chemical effects facilitated by hydrogen bonding, but also retain a substantial number of vacant Pt sites. These results highlight the potential of self-assembled porous phases as a promising avenue for engineering oxide films on metal catalysts.
{"title":"Tuning surface chemistry of inverse catalysts ZnOxHy/Pt(111) without site blocking","authors":"Kaustubh J. Sawant, Junxian Gao, Jeffrey T. Miller, Zhenhua Zeng, Dmitry Zemlyanov, Jeffrey P. Greeley","doi":"10.1016/j.checat.2024.101258","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101258","url":null,"abstract":"In this study, we explore how the formation of self-assembled porous hydroxylated phases provides a strategy to modulate surface chemistry while preserving the number of active sites. Specifically, we investigated graphene-like ZnO films and related Zn<sub>6</sub>O<sub>5</sub>H<sub>5</sub> overlayers on Pt(111) as model inverse catalysts with relevance to industrial catalysis. By combining surface science experiments and density functional theory (DFT) calculations, we demonstrate that the formation of ZnO films minimally affects the adsorption properties of CO, a common probe adsorbate for industrially relevant reactions, while significantly blocking surface Pt sites. By contrast, the porous Zn<sub>6</sub>O<sub>5</sub>H<sub>5</sub> films on Pt not only modulate CO adsorption energies and site preferences, mediated by charge donation and chemical effects facilitated by hydrogen bonding, but also retain a substantial number of vacant Pt sites. These results highlight the potential of self-assembled porous phases as a promising avenue for engineering oxide films on metal catalysts.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"15 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143192391","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-22DOI: 10.1016/j.checat.2024.101239
Árni Björn Höskuldsson, Yasufumi Sakai, Egill Skúlason
Despite intense research efforts both computational and experimental, a catalyst able to electrochemically reduce atmospheric nitrogen to ammonia in aqueous media has not been identified. While rigid protocols have been implemented on the experimental side, a lack of agreement between theory and experiments persists. Here, we critically assess the methodology and assumptions employed in constructing the free energy landscape in the bulk of theoretical studies on the electrochemical nitrogen reduction reaction (NRR) with the aim of contributing to better agreement with experiments. The focus is specifically on the treatment of non-electrochemical reaction steps. Moreover, we discuss the use of machine learning models such as deep neural networks (DNNs) for catalyst discovery and point out common pitfalls. Our work shows the promise of DNNs if they are used correctly but also highlights their limitations and the necessity of high-quality data for training. Finally, we gauge the feasibility of the NRR, using high-entropy alloys as a case study.
{"title":"Modeling electrochemical nitrogen reduction","authors":"Árni Björn Höskuldsson, Yasufumi Sakai, Egill Skúlason","doi":"10.1016/j.checat.2024.101239","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101239","url":null,"abstract":"Despite intense research efforts both computational and experimental, a catalyst able to electrochemically reduce atmospheric nitrogen to ammonia in aqueous media has not been identified. While rigid protocols have been implemented on the experimental side, a lack of agreement between theory and experiments persists. Here, we critically assess the methodology and assumptions employed in constructing the free energy landscape in the bulk of theoretical studies on the electrochemical nitrogen reduction reaction (NRR) with the aim of contributing to better agreement with experiments. The focus is specifically on the treatment of non-electrochemical reaction steps. Moreover, we discuss the use of machine learning models such as deep neural networks (DNNs) for catalyst discovery and point out common pitfalls. Our work shows the promise of DNNs if they are used correctly but also highlights their limitations and the necessity of high-quality data for training. Finally, we gauge the feasibility of the NRR, using high-entropy alloys as a case study.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"33 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-01-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992365","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Particulate photocatalysis (PC) has shown great potential in sustainable chemical synthesis. Until now, developing a scalable PC system remains a major challenge hurdling the practical application of hydrogen peroxide (H2O2) photosynthesis. Here, we report a flexible hydrophobic photocatalyst sheet based on visible-light-responsive bismuth vanadate (BiVO4) photocatalysts with (λ < 520 nm) to achieve flow-transport-dependent cascade photocatalytic H2O2 production. Using dissolved oxygen from the air and deionized water or tap water, the flexible sheets showed solar-to-chemical conversion (STC) efficiency of 0.11%. These BiVO4 photocatalyst sheets were arranged in a 4 × 4-panels array in a 1-m2 flow-by reactor and achieved 1-month outdoor stability under diurnal solar cycles. We utilized this solar-produced H2O2 solution for disinfection, achieving >99.9% inactivation of a coronavirus surrogate in 60 min. Techno-economic analysis (TEA) shows that at 2% STC efficiency, the cost becomes comparable to commercial approaches due to the elimination of transportation, storage, and deployment costs.
{"title":"Hydrogen peroxide photosynthesis from water and air using a scaled-up 1-m2 flow reactor","authors":"Xiaoshan Zheng, Rito Yanagi, Zhenhua Pan, Chong Zhou, Tian Liu, Baoliang Chen, Kenji Katayama, Shu Hu, Chiheng Chu","doi":"10.1016/j.checat.2024.101238","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101238","url":null,"abstract":"Particulate photocatalysis (PC) has shown great potential in sustainable chemical synthesis. Until now, developing a scalable PC system remains a major challenge hurdling the practical application of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) photosynthesis. Here, we report a flexible hydrophobic photocatalyst sheet based on visible-light-responsive bismuth vanadate (BiVO<sub>4</sub>) photocatalysts with (λ < 520 nm) to achieve flow-transport-dependent cascade photocatalytic H<sub>2</sub>O<sub>2</sub> production. Using dissolved oxygen from the air and deionized water or tap water, the flexible sheets showed solar-to-chemical conversion (STC) efficiency of 0.11%. These BiVO<sub>4</sub> photocatalyst sheets were arranged in a 4 × 4-panels array in a 1-m<sup>2</sup> flow-by reactor and achieved 1-month outdoor stability under diurnal solar cycles. We utilized this solar-produced H<sub>2</sub>O<sub>2</sub> solution for disinfection, achieving >99.9% inactivation of a coronavirus surrogate in 60 min. Techno-economic analysis (TEA) shows that at 2% STC efficiency, the cost becomes comparable to commercial approaches due to the elimination of transportation, storage, and deployment costs.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"45 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991221","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-01-21DOI: 10.1016/j.checat.2024.101237
Xi Cao, Shan Ren, Zijuan Yu, Qikui Fan, Qian Lv, Rui Yu, Ang Li, Jian Yang, Junjie Mao
The development of efficient and stable electrocatalysts for CO2 reduction is crucial for sustainable CO production. This study introduces a catalyst where Ni nanoparticles and isolated Ni-N sites are supported on mesoporous nitrogen-doped carbon nanotubes (Ni@N-CNTs), which demonstrates exceptional performance in pH-universal environments. The Ni@N-CNTs catalyst achieves a remarkable CO Faradaic efficiency (FE) of about 95% at a current density of 1,200 mA cm−2 in neutral and alkaline flow cells. Notably, it also maintains high FE (>90%) at current densities ranging from 100 to 900 mA cm−2 in acidic environments. Furthermore, in membrane electrode assembly (MEA), it achieves over 90% CO FE at 700 mA cm−2 with prolonged stability. The catalyst can continuously produce CO with 97.5% purity in a practical setting, highlighting its potential for industrial applications. Mechanism studies indicate that the unique interaction between Ni-N and Ni nanoparticles in the Ni@N-CNTs catalyst optimizes the protonation step, enhancing CO formation.
开发高效、稳定的二氧化碳还原电催化剂是实现二氧化碳可持续生产的关键。本研究介绍了一种催化剂，将Ni纳米颗粒和分离的Ni- n位点负载在介孔氮掺杂碳纳米管上（Ni@N-CNTs），该催化剂在ph通用环境中表现出优异的性能。Ni@N-CNTs催化剂在中性和碱性液流电池中，电流密度为1200 mA cm−2时，CO的法拉第效率（FE）可达95%左右。值得注意的是，在酸性环境中，在电流密度为100至900 mA cm - 2的情况下，它也能保持高FE （>90%）。此外，在膜电极组装（MEA）中，它在700 mA cm - 2下达到90%以上的CO FE，并具有长时间的稳定性。该催化剂在实际环境中可连续生产纯度为97.5%的CO，具有工业应用潜力。机理研究表明，Ni@N-CNTs催化剂中Ni- n和Ni纳米颗粒之间独特的相互作用优化了质子化步骤，促进了CO的形成。
{"title":"Synergistic integration of atomic-scale Ni-N sites and Ni nanoparticles for enhanced protonation in pH-universal electrochemical CO2 reduction","authors":"Xi Cao, Shan Ren, Zijuan Yu, Qikui Fan, Qian Lv, Rui Yu, Ang Li, Jian Yang, Junjie Mao","doi":"10.1016/j.checat.2024.101237","DOIUrl":"https://doi.org/10.1016/j.checat.2024.101237","url":null,"abstract":"The development of efficient and stable electrocatalysts for CO<sub>2</sub> reduction is crucial for sustainable CO production. This study introduces a catalyst where Ni nanoparticles and isolated Ni-N sites are supported on mesoporous nitrogen-doped carbon nanotubes (Ni@N-CNTs), which demonstrates exceptional performance in pH-universal environments. The Ni@N-CNTs catalyst achieves a remarkable CO Faradaic efficiency (FE) of about 95% at a current density of 1,200 mA cm<sup>−2</sup> in neutral and alkaline flow cells. Notably, it also maintains high FE (>90%) at current densities ranging from 100 to 900 mA cm<sup>−2</sup> in acidic environments. Furthermore, in membrane electrode assembly (MEA), it achieves over 90% CO FE at 700 mA cm<sup>−2</sup> with prolonged stability. The catalyst can continuously produce CO with 97.5% purity in a practical setting, highlighting its potential for industrial applications. Mechanism studies indicate that the unique interaction between Ni-N and Ni nanoparticles in the Ni@N-CNTs catalyst optimizes the protonation step, enhancing CO formation.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"45 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-01-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142991174","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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