Facing with the growing demand of wastewater purification in industry and human being, the effect of catalyst on the activation of dissolved oxygen molecule plays a critical role for advanced oxidation processes (AOPs). Surface I atom-doped Bi2WO6 (I-BWO) sheet was successfully synthesized through a two-step hydrothermal method. The decomposition degradation efficiencies of p-chlorophenol and rhodamine B pollutants for the optimized 2I-BWO sample were 14.5 times and 11.0 times than those of the pristine Bi2WO6. The MS results about intermediates explained the mechanism of 4-CP and RhB degradation. Facing with other four organic pollutants such as methylene blue, methyl orange, 4-nitrophenol and tetracycline, the COD removal efficiencies were also observably declined through the photocatalysis. Based on experimental and computational results, the surface I atom caused the disorder of surface structure, forming superior adsorption and activation site of dissolved oxygen molecule. Multiple oxidizing species including superoxide radical, hydroxide radical, singlet oxygen and hydrogen peroxide, were proven to be generated on the modified surface of Bi2WO6 sheet. This study contributes to understanding the impact of in iodine doping on surface structural regulation, thereby facilitating rational design of efficient photocatalysts for AOPs.
随着工业和人类对废水净化需求的不断增长，催化剂对溶解氧分子活化的影响对高级氧化工艺（AOPs）起着至关重要的作用。通过两步水热法成功合成了表面 I 原子掺杂的 Bi2WO6（I-BWO）薄片。优化的 2I-BWO 样品对对氯苯酚和罗丹明 B 污染物的分解降解效率分别是原始 Bi2WO6 的 14.5 倍和 11.0 倍。有关中间产物的质谱结果解释了 4-CP 和 RhB 的降解机理。面对其他四种有机污染物，如亚甲基蓝、甲基橙、4-硝基苯酚和四环素，光催化对 COD 的去除率也明显下降。根据实验和计算结果，表面 I 原子造成了表面结构的紊乱，形成了溶解氧分子的优良吸附和活化位点。实验证明，在改性后的 Bi2WO6 片材表面生成了多种氧化物种，包括超氧自由基、氢氧自由基、单线态氧和过氧化氢。这项研究有助于了解碘掺杂对表面结构调节的影响，从而有助于合理设计用于 AOPs 的高效光催化剂。
{"title":"Effect of surface iodine atom on dissolved oxygen activation for enhanced photocatalytic advanced oxidation processes over Bi2WO6 nanosheet","authors":"Ji-Chao Wang, Haoran Ma, Weina Shi, Wanqing Zhang, Jinyu Wang, Yuxia Hou, Xiaonan Zheng, Jingjie Liu, Junhao Zhao","doi":"10.1016/j.jcat.2024.115909","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115909","url":null,"abstract":"Facing with the growing demand of wastewater purification in industry and human being, the effect of catalyst on the activation of dissolved oxygen molecule plays a critical role for advanced oxidation processes (AOPs). Surface I atom-doped Bi<sub>2</sub>WO<sub>6</sub> (I-BWO) sheet was successfully synthesized through a two-step hydrothermal method. The decomposition degradation efficiencies of p-chlorophenol and rhodamine B pollutants for the optimized 2I-BWO sample were 14.5 times and 11.0 times than those of the pristine Bi<sub>2</sub>WO<sub>6</sub>. The MS results about intermediates explained the mechanism of 4-CP and RhB degradation. Facing with other four organic pollutants such as methylene blue, methyl orange, 4-nitrophenol and tetracycline, the COD removal efficiencies were also observably declined through the photocatalysis. Based on experimental and computational results, the surface I atom caused the disorder of surface structure, forming superior adsorption and activation site of dissolved oxygen molecule. Multiple oxidizing species including superoxide radical, hydroxide radical, singlet oxygen and hydrogen peroxide, were proven to be generated on the modified surface of Bi<sub>2</sub>WO<sub>6</sub> sheet. This study contributes to understanding the impact of in iodine doping on surface structural regulation, thereby facilitating rational design of efficient photocatalysts for AOPs.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"85 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832608","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 : 2024-12-16DOI: 10.1016/j.jcat.2024.115907
Zelin Du, Gen Li, Yawei Liu, Yan Xu, En-Qing Gao, Dawei Zhang
Aerobic oxidation of arylboronic acids under visible light has been intensively explored for synthesis of phenols, for which the need for sacrificial electron-donor agents detracts from the benignancy and sustainability. Here we present the first demonstration of nonsacrificial photocatalytic hydroxylation of arylboronic acids. By turning the electron-poor substrates to electron-rich, the photocatalytic aerobic oxidation proceeds through a mechanism completely different from previous ones, involving the direct oxidation of the aryl-B substrates to aryl radicals through visible-light-induced single-electron transfer to photocatalysts. The protocol not only obviates the need for sacrificial electron donors but also allows efficient reactions in water. It is applicable to various photocatalysts, either homogeneous or heterogeneous. The work provides a green alternative to the traditional methods for synthesis of phenols, and the insight gained from it may open new perspectives for organic photosynthesis that involve aryl radicals.
{"title":"Turning substrates from electron-poor to electron-rich for nonsacrificial aerobic hydroxylation under visible light","authors":"Zelin Du, Gen Li, Yawei Liu, Yan Xu, En-Qing Gao, Dawei Zhang","doi":"10.1016/j.jcat.2024.115907","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115907","url":null,"abstract":"Aerobic oxidation of arylboronic acids under visible light has been intensively explored for synthesis of phenols, for which the need for sacrificial electron-donor agents detracts from the benignancy and sustainability. Here we present the first demonstration of nonsacrificial photocatalytic hydroxylation of arylboronic acids. By turning the electron-poor substrates to electron-rich, the photocatalytic aerobic oxidation proceeds through a mechanism completely different from previous ones, involving the direct oxidation of the aryl-B substrates to aryl radicals through visible-light-induced single-electron transfer to photocatalysts. The protocol not only obviates the need for sacrificial electron donors but also allows efficient reactions in water. It is applicable to various photocatalysts, either homogeneous or heterogeneous. The work provides a green alternative to the traditional methods for synthesis of phenols, and the insight gained from it may open new perspectives for organic photosynthesis that involve aryl radicals.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"49 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832607","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 : 2024-12-16DOI: 10.1016/j.jcat.2024.115903
Valentino Cárdenas-Toledo, Enrique Francés-Poveda, Felipe Barrientos-Barichivic, Jordano Valenzuela, Oscar A. Douglas-Gallardo, Mario E. Flores, Agustín Lara-Sánchez, Oleksandra S. Trofymchuk, Francisca Werlinger, Javier Martínez
Epoxy fatty acids and waste vegetable oils can be strategically utilized as renewable feedstock for the synthesis of novel bio-based oligomers. Herein, we present an efficient synthetic methodology for producing a wide range of bio-oligomers from the ring-opening copolymerization (ROCOP) reaction of linoleic acid-derived epoxides (MLO, methyl linoleate oxide; ELO, ethyl linoleate oxide; ILO, isopropyl linoleate oxide) or epoxidized sunflower oil (ESO) with cyclic anhydrides (such as phthalic anhydride PA, and maleic anhydride MA). The reaction is catalyzed by a wide variety of commercially available amino acids (AAs) along with tetrabutylammonium iodide (TBAI) serving as a cocatalyst. Among the studied AAs as bio-organocatalysts, L-glutamic acid (L-Glu) exhibited the best performance for the preparation of poly(MLO-co-PA), poly(ELO-co-PA), poly(ILO-co-PA), poly(MLO-co-MA), poly(ELO-co-MA), and poly(ILO-co-MA) achieving a 100 % conversion at 80 °C in only 30 min. In contrast, the synthesis of poly(ESO-co-PA) and poly(ESO-co-MA) required 1 h to reach full conversion under the same conditions. The resulting oligomers were extensively characterized by using NMR, FT-IR, GPC, and TGA. Additionally, a set of computational simulations based on density functional theory (DFT) method was also carried out to support our experimental findings. Climbing-image nudged elastic band (CI-NEB) method was employed to find the minimum energy path (MEP) that describes the reaction mechanism associated with the first step of this chemical transformation. The calculated reaction path provides an energetic and atomistic picture of the studied reaction which aims to understand the role of both catalysts.
环氧脂肪酸和废弃植物油可作为合成新型生物基低聚物的可再生原料进行战略性利用。在此，我们介绍一种高效的合成方法，利用亚油酸衍生环氧化物（MLO，亚油酸甲酯氧化物；ELO，亚油酸乙酯氧化物；ILO，亚油酸异丙酯氧化物）或环氧化葵花籽油（ESO）与环状酸酐（如邻苯二甲酸酐 PA 和马来酸酐 MA）的开环共聚（ROCOP）反应生产出多种生物低聚物。该反应由多种市售氨基酸（AA）催化，碘化四丁基铵（TBAI）作为助催化剂。在所研究的生物有机催化剂 AAs 中，L-谷氨酸（L-Glu）在制备聚(MLO-co-PA)、聚(ELO-co-PA)、聚(ILO-co-PA)、聚(MLO-co-MA)、聚(ELO-co-MA)和聚(ILO-co-MA)时表现出最佳性能，在 80 °C 下仅需 30 分钟即可实现 100% 转化。相比之下，在相同条件下合成聚（ESO-co-PA）和聚（ESO-co-MA）需要 1 小时才能达到完全转化。通过使用核磁共振、傅立叶变换红外光谱、气相色谱法和热重分析法对所得低聚物进行了广泛表征。此外，我们还基于密度泛函理论（DFT）方法进行了一系列计算模拟，以支持我们的实验结果。我们采用了爬升图像推移弹性带（CI-NEB）方法来寻找最小能量路径（MEP），该路径描述了与这种化学转化的第一步相关的反应机制。计算出的反应路径提供了所研究反应的能量和原子图景，旨在了解两种催化剂的作用。
{"title":"Amino acids as eco-friendly bio-organocatalysts in ROCOP for the preparation of biobased oligomers from fatty acid epoxides and waste sunflower oil","authors":"Valentino Cárdenas-Toledo, Enrique Francés-Poveda, Felipe Barrientos-Barichivic, Jordano Valenzuela, Oscar A. Douglas-Gallardo, Mario E. Flores, Agustín Lara-Sánchez, Oleksandra S. Trofymchuk, Francisca Werlinger, Javier Martínez","doi":"10.1016/j.jcat.2024.115903","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115903","url":null,"abstract":"Epoxy fatty acids and waste vegetable oils can be strategically utilized as renewable feedstock for the synthesis of novel bio-based oligomers. Herein, we present an efficient synthetic methodology for producing a wide range of bio-oligomers from the ring-opening copolymerization (ROCOP) reaction of linoleic acid-derived epoxides (MLO, methyl linoleate oxide; ELO, ethyl linoleate oxide; ILO, isopropyl linoleate oxide) or epoxidized sunflower oil (ESO) with cyclic anhydrides (such as phthalic anhydride PA, and maleic anhydride MA). The reaction is catalyzed by a wide variety of commercially available amino acids (AAs) along with tetrabutylammonium iodide (TBAI) serving as a cocatalyst. Among the studied AAs as bio-organocatalysts, L-glutamic acid (L-Glu) exhibited the best performance for the preparation of poly(MLO-<em>co</em>-PA), poly(ELO-<em>co</em>-PA), poly(ILO-<em>co</em>-PA), poly(MLO-<em>co</em>-MA), poly(ELO-<em>co</em>-MA), and poly(ILO-<em>co</em>-MA) achieving a 100 % conversion at 80 °C in only 30 min. In contrast, the synthesis of poly(ESO-<em>co</em>-PA) and poly(ESO-<em>co</em>-MA) required 1 h to reach full conversion under the same conditions. The resulting oligomers were extensively characterized by using NMR, FT-IR, GPC, and TGA. Additionally, a set of computational simulations based on density functional theory (DFT) method was also carried out to support our experimental findings. Climbing-image nudged elastic band (CI-NEB) method was employed to find the minimum energy path (MEP) that describes the reaction mechanism associated with the first step of this chemical transformation. The calculated reaction path provides an energetic and atomistic picture of the studied reaction which aims to understand the role of both catalysts.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"24 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142832609","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 : 2024-12-15DOI: 10.1016/j.jcat.2024.115906
Gwonho Yu, Dong Hyeon Mok, Ho Yeon Jang, Hyun Dong Jung, Samira Siahrostami, Seoin Back
As the demand for hydrogen peroxide (H2O2) increases across various industries, there is a growing need for eco-friendly production process to replace the energy-intensive and environmentally polluting anthraquinone process. In particular, the electrochemical production of H2O2 via the two-electron oxygen reduction reaction (2e-ORR) is being highlighted as a promising alternative. However, achieving high selectivity for 2e-ORR over the four-electron reduction reaction (4e-ORR), remains challenging. We introduce an integrative strategy that combines active motifs-based design with a machine learning to discover promising catalysts for electrochemical H2O2 production. Inspired by single-site alloys that destabilize the binding strength of O* adsorbate, thereby improving the 2e-ORR selectivity, we expanded the chemical space through elemental substitution and efficiently explored this expanded chemical space using machine learning methods. By employing these approaches, we discovered active, selective and stable 2e-ORR catalysts that are not present in the existing database and demonstrated better stability compared to the materials within the database. This work highlights the potential of integrating active motifs-based catalyst design with machine learning to efficiently explore the vast chemical space, accelerating the discovery of novel catalysts.
{"title":"Leveraging Machine learning and active motifs-based catalyst design for discovery of oxygen reduction electrocatalysts for hydrogen peroxide production","authors":"Gwonho Yu, Dong Hyeon Mok, Ho Yeon Jang, Hyun Dong Jung, Samira Siahrostami, Seoin Back","doi":"10.1016/j.jcat.2024.115906","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115906","url":null,"abstract":"As the demand for hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) increases across various industries, there is a growing need for eco-friendly production process to replace the energy-intensive and environmentally polluting anthraquinone process. In particular, the electrochemical production of H<sub>2</sub>O<sub>2</sub> via the two-electron oxygen reduction reaction (2e-ORR) is being highlighted as a promising alternative. However, achieving high selectivity for 2e-ORR over the four-electron reduction reaction (4e-ORR), remains challenging. We introduce an integrative strategy that combines active motifs-based design with a machine learning to discover promising catalysts for electrochemical H<sub>2</sub>O<sub>2</sub> production. Inspired by single-site alloys that destabilize the binding strength of O* adsorbate, thereby improving the 2e-ORR selectivity, we expanded the chemical space through elemental substitution and efficiently explored this expanded chemical space using machine learning methods. By employing these approaches, we discovered active, selective and stable 2e-ORR catalysts that are not present in the existing database and demonstrated better stability compared to the materials within the database. This work highlights the potential of integrating active motifs-based catalyst design with machine learning to efficiently explore the vast chemical space, accelerating the discovery of novel catalysts.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"29 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142823225","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}
Heterogeneous electrocatalysis is an advanced tactics to oxidize organic sulfides into value-added products, concurrently being accompanied with hydrogen production in the aqueous electrolyte. However, the insufficient oxidizing ability of redox mediators and competitive oxygen evolution reaction (OER) inhibited the late-stage oxygenation of thioethers to produce sulfones. Herein, a RuO2-loaded Co3O4 electrocatalyst (Ru-Co3O4) was constructed to oxidize thioethers at the potential range of 0.7–0.8 V (vs. Ag/AgCl) at which the OER did not sharply occur, and various sulfoxides and sulfones were produced selectively with moderate to good yields. Mechanism studies revealed that the Ru-Co3O4 electrocatalyst afforded Ru4+ active species and hydroxyl radicals (·OH) at a low potential. The generated RuⅣ/RuⅢ redox couple was responsible for the oxidation of sulfides into sulfur-related cation radicals which then reacted with ·OH and deprotonated to form oxygenation products. This work provided a reasonable proposal for the design of heterogeneous electrocatalysts, which could effectively drive the organic oxygenation reactions.
{"title":"Mechanistic insights into RuⅣ/RuⅢ and ·OH-co-participated selective oxidation of thioethers into sulfoxides and sulfones over a Ru-Co3O4 electrocatalyst","authors":"Ming Xiang, Tianmin Zhang, Weijie Li, Yingjie Ding, Jiaqi Chen, Cheng Fu, Zhaoxiong Yan, Zhihua Xu","doi":"10.1016/j.jcat.2024.115905","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115905","url":null,"abstract":"Heterogeneous electrocatalysis is an advanced tactics to oxidize organic sulfides into value-added products, concurrently being accompanied with hydrogen production in the aqueous electrolyte. However, the insufficient oxidizing ability of redox mediators and competitive oxygen evolution reaction (OER) inhibited the late-stage oxygenation of thioethers to produce sulfones. Herein, a RuO<sub>2</sub>-loaded Co<sub>3</sub>O<sub>4</sub> electrocatalyst (Ru-Co<sub>3</sub>O<sub>4</sub>) was constructed to oxidize thioethers at the potential range of 0.7–0.8 V (vs. Ag/AgCl) at which the OER did not sharply occur, and various sulfoxides and sulfones were produced selectively with moderate to good yields. Mechanism studies revealed that the Ru-Co<sub>3</sub>O<sub>4</sub> electrocatalyst afforded Ru<sup>4+</sup> active species and hydroxyl radicals (·OH) at a low potential. The generated Ru<sup>Ⅳ</sup>/Ru<sup>Ⅲ</sup> redox couple was responsible for the oxidation of sulfides into sulfur-related cation radicals which then reacted with ·OH and deprotonated to form oxygenation products. This work provided a reasonable proposal for the design of heterogeneous electrocatalysts, which could effectively drive the organic oxygenation reactions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"28 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142823287","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 : 2024-12-14DOI: 10.1016/j.jcat.2024.115898
Weijie Zhang, Bingxin Wang, Luting Liu, Xinye Luo, Quan Wan, Bing Yi, Weijie Chi, Hai Yang
Long-lived triplet excited states have been regarded as active species in the implementation of photochemical strategies owing to their associated high energy and electron transfer abilities, yet it was still challenging to fulfill this in polymeric photocatalysis. Herein, we formulated a built-in donor–acceptor interaction control strategy to prolong the excited-state lifetime in conjugated organic polymers (COPs) by minimizing the exciton binding energy in the first excited state. The resultant COPs decorated with tris([1,2,4]triazolo)[4,3-a:4′,3′-c:4′’,3′’-e][1,3,5]triazine exhibited excellent activities in photocatalytic amide formation (95 % yield), which was much higher than that of triazine rings as an analogous moiety(66 % yield) owing to its prolonged triplet-state lifetimes (τ = 30.5 µs) and the improved photo-induced charge separation efficiency. These results not only demonstrate the feasibility of realizing triplet excited states for heterogeneous photocatalysis through molecular engineering but also offers insights into energy and electron transfer at the molecular level.
{"title":"Prolonging triplet-state lifetimes to boost the energy and electron transfer in conjugated organic polymers for photocatalytic amide formation","authors":"Weijie Zhang, Bingxin Wang, Luting Liu, Xinye Luo, Quan Wan, Bing Yi, Weijie Chi, Hai Yang","doi":"10.1016/j.jcat.2024.115898","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115898","url":null,"abstract":"Long-lived triplet excited states have been regarded as active species in the implementation of photochemical strategies owing to their associated high energy and electron transfer abilities, yet it was still challenging to fulfill this in polymeric photocatalysis. Herein, we formulated a built-in donor–acceptor interaction control strategy to prolong the excited-state lifetime in conjugated organic polymers (COPs) by minimizing the exciton binding energy in the first excited state. The resultant COPs decorated with tris([1,2,4]triazolo)[4,3-a:4′,3′-c:4′’,3′’-e][1,3,5]triazine exhibited excellent activities in photocatalytic amide formation (95 % yield), which was much higher than that of triazine rings as an analogous moiety(66 % yield) owing to its prolonged triplet-state lifetimes (τ = 30.5 µs) and the improved photo-induced charge separation efficiency. These results not only demonstrate the feasibility of realizing triplet excited states for heterogeneous photocatalysis through molecular engineering but also offers insights into energy and electron transfer at the molecular level.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"20 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820648","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 : 2024-12-13DOI: 10.1016/j.jcat.2024.115902
Atharva S. Burte, Advaith Nair, Lars C. Grabow, Paul J. Dauenhauer, Susannah L. Scott, Omar A. Abdelrahman
The ability to quantitatively compare newly evolving catalytic materials and technologies is hindered by the widespread availability of catalytic data collected in a consistent manner. While certain catalytic chemistries have been widely studied across decades of scientific research, quantitative comparisons based on literature information is hindered by variability in reaction conditions, types of reported data, and reporting procedures. Here, we present CatTestHub, an open-access database dedicated to benchmarking experimental heterogeneous catalysis data. Combining systematically reported catalytic activity data for selected probe chemistries, with relevant material characterization information, and reactor configuration, the database provides a collection of catalytic benchmarks for distinct classes of active site functionality. Through key choices in data access, availability, and traceability, CatTestHub seeks to balance the fundamental information needs of chemical catalysis and the FAIR data design principles. Details of the database architecture and the means through which to navigate it are presented, highlighting examples of catalytic insights readily drawn from the available benchmarking data. In its current iteration, CatTestHub spans over 250 unique experimental data points, collected over 24 solid catalysts, that facilitated the turnover of 3 distinct catalytic chemistries. A roadmap is presented through which to expand the open-access platform that serves as a community wide benchmark, primarily through continuous addition of kinetic information on select catalytic systems by members of the heterogeneous catalysis community at large.
{"title":"CatTestHub: A benchmarking database of experimental heterogeneous catalysis for evaluating advanced materials","authors":"Atharva S. Burte, Advaith Nair, Lars C. Grabow, Paul J. Dauenhauer, Susannah L. Scott, Omar A. Abdelrahman","doi":"10.1016/j.jcat.2024.115902","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115902","url":null,"abstract":"The ability to quantitatively compare newly evolving catalytic materials and technologies is hindered by the widespread availability of catalytic data collected in a consistent manner. While certain catalytic chemistries have been widely studied across decades of scientific research, quantitative comparisons based on literature information is hindered by variability in reaction conditions, types of reported data, and reporting procedures. Here, we present CatTestHub, an open-access database dedicated to benchmarking experimental heterogeneous catalysis data. Combining systematically reported catalytic activity data for selected probe chemistries, with relevant material characterization information, and reactor configuration, the database provides a collection of catalytic benchmarks for distinct classes of active site functionality. Through key choices in data access, availability, and traceability, CatTestHub seeks to balance the fundamental information needs of chemical catalysis and the FAIR data design principles. Details of the database architecture and the means through which to navigate it are presented, highlighting examples of catalytic insights readily drawn from the available benchmarking data. In its current iteration, CatTestHub spans over 250 unique experimental data points, collected over 24 solid catalysts, that facilitated the turnover of 3 distinct catalytic chemistries. A roadmap is presented through which to expand the open-access platform that serves as a community wide benchmark, primarily through continuous addition of kinetic information on select catalytic systems by members of the heterogeneous catalysis community at large.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"29 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142820654","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 : 2024-12-12DOI: 10.1016/j.jcat.2024.115900
Peng Gao, Zewen Shen, Yana Chen, Tao Jiang, Zhuoyu Ji, Guixia Zhao, Junrong Yue, Yezi Hu, Xiangke Wang, Xiubing Huang, Martin Muhler, Lisha Yin
Depleted uranium as a mildly radioactive waste product from the 235U enrichment process is stocked worldwide, which can be considered as ideal photocatalyst for light-driven photo-redox reactions. Under light irradiation, the generated excited-state *UO22+ possesses strong oxidative ability and long-lived fluorescence lifetime via ligand to metal charge transfer (LMCT), which can be effectively quenched by organic substrates via hydrogen atom transfer (HAT) and single electron transfer (SET) processes. The applications of both homogeneous and heterogeneous uranyl-based photocatalysts (including uranyl salts, uranyl-loading composite catalysts, uranyl-based complexes, and uranyl-based metal–organic frameworks) exhibit their advances in unique electronic structure, excellent photochemical properties, and outstanding photocatalytic performance in organic photo-transformation reactions. This review is to highlight the light-driven transformation of organic substances over various types of homogeneous and heterogeneous uranyl-based photocatalysts. The current research survey verifies that spent nuclear waste possesses great potential to construct efficient photocatalysts for light-driven organics transformation.
{"title":"A review on uranyl-based photocatalysts in photocatalytic organic transformation","authors":"Peng Gao, Zewen Shen, Yana Chen, Tao Jiang, Zhuoyu Ji, Guixia Zhao, Junrong Yue, Yezi Hu, Xiangke Wang, Xiubing Huang, Martin Muhler, Lisha Yin","doi":"10.1016/j.jcat.2024.115900","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115900","url":null,"abstract":"Depleted uranium as a mildly radioactive waste product from the <sup>235</sup>U enrichment process is stocked worldwide, which can be considered as ideal photocatalyst for light-driven photo-redox reactions. Under light irradiation, the generated excited-state *UO<sub>2</sub><sup>2+</sup> possesses strong oxidative ability and long-lived fluorescence lifetime via ligand to metal charge transfer (LMCT), which can be effectively quenched by organic substrates via hydrogen atom transfer (HAT) and single electron transfer (SET) processes. The applications of both homogeneous and heterogeneous uranyl-based photocatalysts (including uranyl salts, uranyl-loading composite catalysts, uranyl-based complexes, and uranyl-based metal–organic frameworks) exhibit their advances in unique electronic structure, excellent photochemical properties, and outstanding photocatalytic performance in organic photo-transformation reactions. This review is to highlight the light-driven transformation of organic substances over various types of homogeneous and heterogeneous uranyl-based photocatalysts. The current research survey verifies that spent nuclear waste possesses great potential to construct efficient photocatalysts for light-driven organics transformation.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"29 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142816352","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}
This article describes the development of a stable and reusable diatomic cobalt catalyst for the synthesis of various quinazoline derivatives via the dehydrogenation cyclization reaction of anthranilic alcohol with amidine in a simple and environmental friendly manner. Crystallographic studies reveal that the superior catalytic reactivity can be attributed to the synergistic cooperation between the adjacent cobalt active centers within a confined domain for the co-adsorption and co-activation of substrates. This work provides new insights into the application of heterogeneous catalysts in organic synthesis.
{"title":"Diatomic cobalt–catalyzed cyclization of o-aminobenzyl alcohol with amidine for the synthesis of quinazolines","authors":"Guozhang Fu, Yunong Li, Zhuoqun Hou, Shasha Wang, Shaohua Jiang, Tianxiang Chen, Tsz Woon Benedict Lo, Xiuwen Chen","doi":"10.1016/j.jcat.2024.115889","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115889","url":null,"abstract":"This article describes the development of a stable and reusable diatomic cobalt catalyst for the synthesis of various quinazoline derivatives via the dehydrogenation cyclization reaction of anthranilic alcohol with amidine in a simple and environmental friendly manner. Crystallographic studies reveal that the superior catalytic reactivity can be attributed to the synergistic cooperation between the adjacent cobalt active centers within a confined domain for the co-adsorption and co-activation of substrates. This work provides new insights into the application of heterogeneous catalysts in organic synthesis.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"10 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142804821","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 : 2024-12-10DOI: 10.1016/j.jcat.2024.115897
Yiwei Zhou, Jian Zhao, Hairui Guo, Cheng Wang
Aldehydes ammoxidation is a green and promising route for selective synthesis of nitrile, but developing low-cost and efficient catalytic system under mild condition remains a challenge. Herein, we explore a novel catalytic system where the designed Ni(OH)2/TiO2 p-n heterojunction catalyst could efficiently drive aldehydes ammoxidation with NH3·H2O and O2 at ambient temperature and pressure by using visible-light as the only energy input. The superoxide (•O2–) generated by reducing O2 with photogenerated electrons and amino radicals (•NHx) produced by oxidizing NH3·H2O with photogenerated holes, are successfully identified as key species for the formation of nitriles. Meanwhile, •NHx and •O2– radicals individually work on the formation of the intermediate aldimine intermediate and its oxidation to nitrile. The performance of the engineered Ni(OH)2/TiO2 p-n heterojunctions in the reaction process is much more superior to other catalyst systems. This study develops nitrile synthesis route under mild conditions and present new opportunities for constructing low-cost photocatalyst for chemical synthesis. It also provides a better understanding of the radical species and how they work in aldehydes ammoxidation reactions.
{"title":"Visible-light-driven aldehyde ammoxidation to nitrile via •O2– and •NHx radicals generation over Ni(OH)2/TiO2 p-n heterojunctions","authors":"Yiwei Zhou, Jian Zhao, Hairui Guo, Cheng Wang","doi":"10.1016/j.jcat.2024.115897","DOIUrl":"https://doi.org/10.1016/j.jcat.2024.115897","url":null,"abstract":"Aldehydes ammoxidation is a green and promising route for selective synthesis of nitrile, but developing low-cost and efficient catalytic system under mild condition remains a challenge. Herein, we explore a novel catalytic system where the designed Ni(OH)<sub>2</sub>/TiO<sub>2</sub> p-n heterojunction catalyst could efficiently drive aldehydes ammoxidation with NH<sub>3</sub>·H<sub>2</sub>O and O<sub>2</sub> at ambient temperature and pressure by using visible-light as the only energy input. The superoxide (<sup>•</sup>O<sub>2</sub><sup>–</sup>) generated by reducing O<sub>2</sub> with photogenerated electrons and amino radicals (<sup>•</sup>NH<sub>x</sub>) produced by oxidizing NH<sub>3</sub>·H<sub>2</sub>O with photogenerated holes, are successfully identified as key species for the formation of nitriles. Meanwhile, <sup>•</sup>NH<sub>x</sub> and <sup>•</sup>O<sub>2</sub><sup>–</sup> radicals individually work on the formation of the intermediate aldimine intermediate and its oxidation to nitrile. The performance of the engineered Ni(OH)<sub>2</sub>/TiO<sub>2</sub> p-n heterojunctions in the reaction process is much more superior to other catalyst systems. This study develops nitrile synthesis route under mild conditions and present new opportunities for constructing low-cost photocatalyst for chemical synthesis. It also provides a better understanding of the radical species and how they work in aldehydes ammoxidation reactions.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"48 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2024-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142809767","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：