Pub Date : 2024-11-01DOI: 10.1016/S1872-2067(24)60126-9
Long Song , Jingqi Chi , Junheng Tang , Xiaobin Liu , Zhenyu Xiao , Zexing Wu , Lei Wang
At present, seawater electrolysis powered by renewable energy stands as a crucial method for the industrial production of hydrogen. Given the abundance of seawater and its inherently high conductivity, seawater electrolysis earns an increasing interest. Nonetheless, challenges remain, such as the competitive chloride oxidation reaction (COR) caused by chloride ions (Cl‒) and the corrosion of active sites, which hinder the industrial seawater electrolysis. In this review, we initially outline four design strategies aimed at avoiding the occurrence of COR: designing selective oxygen evolution reaction (OER) active sites, anti-corrosion strategies, small molecules oxidize reaction (SMOR) and adjusting electrolyte. Specifically, we compile approaches to enhance the OER selectivity and corrosion resistance in seawater electrolysis, including introducing anion buffer layer. Subsequently, we categorize reported OER catalysts based on their composition and summarize the mechanism underlying their high activity and stability. In conclusion, we address the future challenges and prospects of industrializing seawater electrolysis.
目前，以可再生能源为动力的海水电解是工业制氢的重要方法。鉴于海水的丰富性及其固有的高导电性，海水电解越来越受到人们的关注。然而，挑战依然存在，例如氯离子（Cl-）引起的竞争性氯氧化反应（COR）和活性位点的腐蚀，这些都阻碍了工业海水电解。在本综述中，我们首先概述了旨在避免发生 COR 的四种设计策略：设计选择性氧进化反应（OER）活性位点、防腐蚀策略、小分子氧化反应（SMOR）和调整电解质。具体而言，我们梳理了提高海水电解中氧进化反应选择性和耐腐蚀性的方法，包括引入阴离子缓冲层。随后，我们根据已报道的 OER 催化剂的组成对其进行了分类，并总结了其高活性和高稳定性的机理。最后，我们探讨了海水电解工业化的未来挑战和前景。
{"title":"Anode design principles for efficient seawater electrolysis and inhibition of chloride oxidation","authors":"Long Song , Jingqi Chi , Junheng Tang , Xiaobin Liu , Zhenyu Xiao , Zexing Wu , Lei Wang","doi":"10.1016/S1872-2067(24)60126-9","DOIUrl":"10.1016/S1872-2067(24)60126-9","url":null,"abstract":"<div><div>At present, seawater electrolysis powered by renewable energy stands as a crucial method for the industrial production of hydrogen. Given the abundance of seawater and its inherently high conductivity, seawater electrolysis earns an increasing interest. Nonetheless, challenges remain, such as the competitive chloride oxidation reaction (COR) caused by chloride ions (Cl<sup>‒</sup>) and the corrosion of active sites, which hinder the industrial seawater electrolysis. In this review, we initially outline four design strategies aimed at avoiding the occurrence of COR: designing selective oxygen evolution reaction (OER) active sites, anti-corrosion strategies, small molecules oxidize reaction (SMOR) and adjusting electrolyte. Specifically, we compile approaches to enhance the OER selectivity and corrosion resistance in seawater electrolysis, including introducing anion buffer layer. Subsequently, we categorize reported OER catalysts based on their composition and summarize the mechanism underlying their high activity and stability. In conclusion, we address the future challenges and prospects of industrializing seawater electrolysis.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"66 ","pages":"Pages 53-75"},"PeriodicalIF":15.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699768","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 : 2024-11-01DOI: 10.1016/S1872-2067(24)60129-4
Shilei Wei , Hang Hua , Qingxuan Ren , Jingshan Luo
The electrochemical reduction of CO2 holds considerable promise in combating global climate change while yielding valuable chemical commodities. Membrane electrode assemblies operating within acidic electrolyte have exhibited noteworthy advancements in CO2 utilization efficiency, albeit encountering formidable competition from the hydrogen evolution reaction. In our investigation, we introduced a silicate buffer layer, which yielded exceptional outcomes even using strong acid electrolyte. Notably, our approach yielded a CO Faradic efficiency of 90% and reached a substantial current density of 400 mA cm–2. Furthermore, our system displayed remarkable stability over a 12-hour duration, and achieved a high single-pass-conversion efficiency of 67%. Leveraging in-situ Raman analysis, we attributed these performance enhancements to the augmented CO2 adsorption and localized alkaline environment facilitated by the incorporation of the silicate buffer layer. We think the addition of buffer layer to adjust the microenvironment is essential to achieve high performance and keep stable in acid condition.
二氧化碳的电化学还原在应对全球气候变化方面大有可为，同时还能产生宝贵的化工产品。在酸性电解质中运行的膜电极组件在二氧化碳利用效率方面取得了显著进步，尽管遇到了氢进化反应的激烈竞争。在我们的研究中，我们引入了硅酸盐缓冲层，即使使用强酸电解质也能产生卓越的效果。值得注意的是，我们的方法产生了 90% 的二氧化碳法拉第效率，并达到了 400 mA cm-2 的巨大电流密度。此外，我们的系统在 12 小时的持续时间内表现出卓越的稳定性，单次转换效率高达 67%。通过原位拉曼分析，我们将这些性能提升归因于硅酸盐缓冲层的加入促进了二氧化碳的吸附和局部碱性环境。我们认为，添加缓冲层来调节微环境对于实现高性能和在酸性条件下保持稳定至关重要。
{"title":"Enhanced electrochemical carbon dioxide reduction in membrane electrode assemblies with acidic electrolytes through a silicate buffer layer","authors":"Shilei Wei , Hang Hua , Qingxuan Ren , Jingshan Luo","doi":"10.1016/S1872-2067(24)60129-4","DOIUrl":"10.1016/S1872-2067(24)60129-4","url":null,"abstract":"<div><div>The electrochemical reduction of CO<sub>2</sub> holds considerable promise in combating global climate change while yielding valuable chemical commodities. Membrane electrode assemblies operating within acidic electrolyte have exhibited noteworthy advancements in CO<sub>2</sub> utilization efficiency, albeit encountering formidable competition from the hydrogen evolution reaction. In our investigation, we introduced a silicate buffer layer, which yielded exceptional outcomes even using strong acid electrolyte. Notably, our approach yielded a CO Faradic efficiency of 90% and reached a substantial current density of 400 mA cm<sup>–2</sup>. Furthermore, our system displayed remarkable stability over a 12-hour duration, and achieved a high single-pass-conversion efficiency of 67%. Leveraging <em>in-situ</em> Raman analysis, we attributed these performance enhancements to the augmented CO<sub>2</sub> adsorption and localized alkaline environment facilitated by the incorporation of the silicate buffer layer. We think the addition of buffer layer to adjust the microenvironment is essential to achieve high performance and keep stable in acid condition.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"66 ","pages":"Pages 139-145"},"PeriodicalIF":15.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699771","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 : 2024-11-01DOI: 10.1016/S1872-2067(24)60157-9
Ya'nan Xia , Jingqi Chi , Junheng Tang , Xiaobin Liu , Zhenyu Xiao , Jianping Lai , Lei Wang
Renewable energy conversion as well as water electrolysis technologies are constrained by the fact that kinetics are always slow in the electrocatalytic oxygen evolution reaction (OER). There are numerous means and strategies for the enhancement of OER activity. In this paper, we systematically review the important role of anionic vacancies in enhancing the OER activity of catalysts: increasing catalyst conductivity, improving electrical conductivity, and enhancing intermediate adsorption. In order to better detect the presence of vacancies in the samples, the principle of vacancy detection is reviewed in detail in terms of both spectroscopic and microscopic characterization, and the methods of vacancy formation as well as the factors influencing the concentration of vacancies are summarized in detail. In addition, the challenges and new directions for the study of anionic vacancies are provided.
可再生能源转换和水电解技术受到电催化氧进化反应（OER）动力学缓慢这一事实的制约。提高氧催化反应活性的方法和策略有很多。在本文中，我们系统地回顾了阴离子空位在增强催化剂 OER 活性方面的重要作用：提高催化剂导电性、改善导电性和增强中间体吸附性。为了更好地检测样品中是否存在空位，本文从光谱和显微表征两方面详细回顾了空位检测的原理，并详细总结了空位形成的方法以及影响空位浓度的因素。此外，还提出了阴离子空位研究的挑战和新方向。
{"title":"Research progress of anionic vacancies in electrocatalysts for oxygen evolution reaction","authors":"Ya'nan Xia , Jingqi Chi , Junheng Tang , Xiaobin Liu , Zhenyu Xiao , Jianping Lai , Lei Wang","doi":"10.1016/S1872-2067(24)60157-9","DOIUrl":"10.1016/S1872-2067(24)60157-9","url":null,"abstract":"<div><div>Renewable energy conversion as well as water electrolysis technologies are constrained by the fact that kinetics are always slow in the electrocatalytic oxygen evolution reaction (OER). There are numerous means and strategies for the enhancement of OER activity. In this paper, we systematically review the important role of anionic vacancies in enhancing the OER activity of catalysts: increasing catalyst conductivity, improving electrical conductivity, and enhancing intermediate adsorption. In order to better detect the presence of vacancies in the samples, the principle of vacancy detection is reviewed in detail in terms of both spectroscopic and microscopic characterization, and the methods of vacancy formation as well as the factors influencing the concentration of vacancies are summarized in detail. In addition, the challenges and new directions for the study of anionic vacancies are provided.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"66 ","pages":"Pages 110-138"},"PeriodicalIF":15.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699770","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 : 2024-11-01DOI: 10.1016/S1872-2067(24)60143-9
Wenjuan Zhang , Gang Liu
H2O2 is an environmentally friendly oxidant and a promising energy-containing molecule widely applied in industrial production, environmental remediation, and as a potential carrier for energy storage. Solar-driven conversion of earth-abundant H2O and O2 is the most ideal method for producing H2O2. Due to poor separation of photogenerated charge carriers in semiconductors, sacrificial reagents such as ethanol are typically added to consume photogenerated holes, but this is not an energy storage process. Therefore, developing efficient photocatalysts for direct H2O2 production from H2O and O2 without sacrificial agents is crucial for sustainable energy conversion. Organic framework materials, due to their customizable structures, have gained traction in the photosynthesis of H2O2 from pure H2O and O2. A series of functionalized molecules have been introduced as building blocks into organic frameworks to enhance the H2O2 production performance, but their key roles in performance and reaction pathways have not been summarized in detail so far. This review aims to address this gap and elucidate the relationship between the structure and performance of organic framework photocatalysts, providing insights and guidance for the development of efficient photocatalysts.
{"title":"Solar-driven H2O2 synthesis from H2O and O2 over molecular engineered organic framework photocatalysts","authors":"Wenjuan Zhang , Gang Liu","doi":"10.1016/S1872-2067(24)60143-9","DOIUrl":"10.1016/S1872-2067(24)60143-9","url":null,"abstract":"<div><div>H<sub>2</sub>O<sub>2</sub> is an environmentally friendly oxidant and a promising energy-containing molecule widely applied in industrial production, environmental remediation, and as a potential carrier for energy storage. Solar-driven conversion of earth-abundant H<sub>2</sub>O and O<sub>2</sub> is the most ideal method for producing H<sub>2</sub>O<sub>2</sub>. Due to poor separation of photogenerated charge carriers in semiconductors, sacrificial reagents such as ethanol are typically added to consume photogenerated holes, but this is not an energy storage process. Therefore, developing efficient photocatalysts for direct H<sub>2</sub>O<sub>2</sub> production from H<sub>2</sub>O and O<sub>2</sub> without sacrificial agents is crucial for sustainable energy conversion. Organic framework materials, due to their customizable structures, have gained traction in the photosynthesis of H<sub>2</sub>O<sub>2</sub> from pure H<sub>2</sub>O and O<sub>2</sub>. A series of functionalized molecules have been introduced as building blocks into organic frameworks to enhance the H<sub>2</sub>O<sub>2</sub> production performance, but their key roles in performance and reaction pathways have not been summarized in detail so far. This review aims to address this gap and elucidate the relationship between the structure and performance of organic framework photocatalysts, providing insights and guidance for the development of efficient photocatalysts.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"66 ","pages":"Pages 76-109"},"PeriodicalIF":15.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699769","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 : 2024-11-01DOI: 10.1016/S1872-2067(24)60132-4
Lu Zhang , Hourui Zhang , Dongyang Zhu , Zihan Fu , Shuangshi Dong , Cong Lyu
Covalent organic frameworks (COFs) have attracted attention as photocatalysts, however, low electron transfer and reactive oxygen species (ROS) generation still hinder their photocatalytic application. In this work, we construct multivariate donor-acceptor (D-A) heterojunctions in the covalent organic frameworks by synchronously introducing electron-withdrawing and donating substituents. Importantly, the optoelectronic characteristics and visible-light photocatalytic performance were improved with the increase of the electron donor carbon chains in multivariate D-A COFs. Combining in-situ characterization with theoretical calculations, the charge carrier separation and transfer efficiency, •O2– generation and conversion, and the energy barrier of the rate determination steps related to the formation of *OH and *OOH, can be well regulated by the multivariate D-A COFs. More importantly, the ortho-carbon atom of the Br and OCH3 group-linked benzene rings and the imine bond (–C=N–) in COF-Br@OCH3 were activated to produce the key *OH and *OOH intermediates for effectively reducing the energy barrier of H2O oxidation and O2 reduction. This work provides valuable insights into the precise design and synthesis of COFs-based catalysts and the regulation of electron transfer and ROS generation by modulating the electron-withdrawing and donating substituents for highly efficient visible-light photocatalytic degradation of refractory organic pollutants.
{"title":"Construction of multivariate donor-acceptor heterojunction in covalent organic frameworks for enhanced photocatalytic oxidation: Regulating electron transfer and superoxide radical generation","authors":"Lu Zhang , Hourui Zhang , Dongyang Zhu , Zihan Fu , Shuangshi Dong , Cong Lyu","doi":"10.1016/S1872-2067(24)60132-4","DOIUrl":"10.1016/S1872-2067(24)60132-4","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) have attracted attention as photocatalysts, however, low electron transfer and reactive oxygen species (ROS) generation still hinder their photocatalytic application. In this work, we construct multivariate donor-acceptor (D-A) heterojunctions in the covalent organic frameworks by synchronously introducing electron-withdrawing and donating substituents. Importantly, the optoelectronic characteristics and visible-light photocatalytic performance were improved with the increase of the electron donor carbon chains in multivariate D-A COFs. Combining <em>in-situ</em> characterization with theoretical calculations, the charge carrier separation and transfer efficiency, •O<sub>2</sub><sup>–</sup> generation and conversion, and the energy barrier of the rate determination steps related to the formation of *OH and *OOH, can be well regulated by the multivariate D-A COFs. More importantly, the ortho-carbon atom of the Br and OCH<sub>3</sub> group-linked benzene rings and the imine bond (–C=N–) in COF-Br@OCH<sub>3</sub> were activated to produce the key *OH and *OOH intermediates for effectively reducing the energy barrier of H<sub>2</sub>O oxidation and O<sub>2</sub> reduction. This work provides valuable insights into the precise design and synthesis of COFs-based catalysts and the regulation of electron transfer and ROS generation by modulating the electron-withdrawing and donating substituents for highly efficient visible-light photocatalytic degradation of refractory organic pollutants.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"66 ","pages":"Pages 181-194"},"PeriodicalIF":15.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699775","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 : 2024-11-01DOI: 10.1016/S1872-2067(24)60123-3
Siyu Chen, Jingqi Guan
Ammonia is a carrier of high energy density and a good hydrogen storage substance. The Haber-Bosch process accounts for 90% of the world's ammonia production, which relies on natural gas and fossil resources as energy sources, not only polluting the ecological environment, but also accelerating the consumption of resources. To explore new ways to synthesize ammonia and reduce carbon emissions, electrocatalytic nitrogen reduction reaction (NRR) to produce ammonia has been emerged owing to the advantages of environmental protection, low energy consumption and mild reaction conditions. Here, we systematize the NRR mechanisms, including dissociation mechanism, association mechanism (involving distal pathway, alternative path, and enzymatic mechanism), and Mars-van Krevelen mechanism. Then, theoretical calculations, performance parameters, synthesis methods, and types of NRR electrocatalysts are introduced in detail. Moreover, effective strategies to optimize the electronic structures of NRR electrocatalysts are emphatically discussed, including d-band center modulation (involving monoatomic dispersion, doping strategy, defect engineering, interface engineering, and strain effect), p-band center modulation, and other regulation strategies (involving construction of heterojunction, electron spin state modulation, phase interface engineering, and lithium ion mediation). Furthermore, we introduce NRR-related cell design and development. In addition, we evaluate relevant NRR experimental techniques, including N adsorption characterization techniques and methods for identification of active sites. Finally, the future challenges and opportunities concerning the improvement of NRR catalysts are outlined.
氨是一种能量密度很高的载体，也是一种很好的储氢物质。哈伯-博什法合成氨占世界合成氨产量的 90%，该工艺依赖天然气和化石资源作为能源，不仅污染生态环境，而且加速资源消耗。为了探索合成氨和减少碳排放的新途径，电催化氮还原反应（NRR）以其环保、能耗低、反应条件温和等优点，成为生产合成氨的新方法。在此，我们系统地介绍了氮还原反应的机理，包括解离机理、关联机理（涉及远端途径、替代途径和酶促机理）以及 Mars-van Krevelen 机理。然后，详细介绍了 NRR 电催化剂的理论计算、性能参数、合成方法和类型。此外，还重点讨论了优化 NRR 电催化剂电子结构的有效策略，包括 d 波段中心调控（涉及单原子分散、掺杂策略、缺陷工程、界面工程和应变效应）、p 波段中心调控和其他调控策略（涉及异质结构建、电子自旋态调控、相界面工程和锂离子调解）。此外，我们还介绍了与 NRR 相关的电池设计和开发。此外，我们还评估了相关的 NRR 实验技术，包括 N 吸附表征技术和活性位点识别方法。最后，我们还概述了改进氮还原催化剂的未来挑战和机遇。
{"title":"Structural regulation strategies of nitrogen reduction electrocatalysts","authors":"Siyu Chen, Jingqi Guan","doi":"10.1016/S1872-2067(24)60123-3","DOIUrl":"10.1016/S1872-2067(24)60123-3","url":null,"abstract":"<div><div>Ammonia is a carrier of high energy density and a good hydrogen storage substance. The Haber-Bosch process accounts for 90% of the world's ammonia production, which relies on natural gas and fossil resources as energy sources, not only polluting the ecological environment, but also accelerating the consumption of resources. To explore new ways to synthesize ammonia and reduce carbon emissions, electrocatalytic nitrogen reduction reaction (NRR) to produce ammonia has been emerged owing to the advantages of environmental protection, low energy consumption and mild reaction conditions. Here, we systematize the NRR mechanisms, including dissociation mechanism, association mechanism (involving distal pathway, alternative path, and enzymatic mechanism), and Mars-van Krevelen mechanism. Then, theoretical calculations, performance parameters, synthesis methods, and types of NRR electrocatalysts are introduced in detail. Moreover, effective strategies to optimize the electronic structures of NRR electrocatalysts are emphatically discussed, including <em>d</em>-band center modulation (involving monoatomic dispersion, doping strategy, defect engineering, interface engineering, and strain effect), <em>p</em>-band center modulation, and other regulation strategies (involving construction of heterojunction, electron spin state modulation, phase interface engineering, and lithium ion mediation). Furthermore, we introduce NRR-related cell design and development. In addition, we evaluate relevant NRR experimental techniques, including N adsorption characterization techniques and methods for identification of active sites. Finally, the future challenges and opportunities concerning the improvement of NRR catalysts are outlined.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"66 ","pages":"Pages 20-52"},"PeriodicalIF":15.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699767","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 : 2024-11-01DOI: 10.1016/S1872-2067(24)60134-8
Zheng Li , Yuanyuan Dong , Ying Zeng , Mo Zhang , Hongjin Lv , Guo-Yu Yang
The selective oxidation of para-xylene (PX) to terephthalic acid (TPA) has received increasing attention due to the industrial applications of TPA. However, the oxidation of the C(sp3)‒H bond of PX is still a main challenge because of the higher bond dissociation energy. Herein, an efficient photocatalytic system for the oxidation of PX to TPA was developed by using tetrabutylammonium decatungstate (TBADT) photocatalyst using atmospheric oxygen as oxidant and 365 nm LED light irradiation. The resulting TPA product was easily separated from the post-reaction solution through simple filtration treatment with a 93.4% yield in CH3CN (37.5% 1 mol L−1 HCl) solvent after 19-h photocatalysis. Given the easy separation of TPA and the excellent recycling stability of TBADT, a continuous-flow photoreactor was successfully designed with promising prospect for potential industrial application. Mechanistic studies elucidated that the presence of HCl additive benefits the structural integrity of [W10O32]4− anions and the transition from excited states [W10O32]4−* to wO active species, leading to enhanced photooxidation performance.
{"title":"A continuous-flow photocatalytic system for highly selective oxidation of p-xylene to terephthalic acid by decatungstate catalyst","authors":"Zheng Li , Yuanyuan Dong , Ying Zeng , Mo Zhang , Hongjin Lv , Guo-Yu Yang","doi":"10.1016/S1872-2067(24)60134-8","DOIUrl":"10.1016/S1872-2067(24)60134-8","url":null,"abstract":"<div><div>The selective oxidation of para-xylene (PX) to terephthalic acid (TPA) has received increasing attention due to the industrial applications of TPA. However, the oxidation of the C(<em>sp</em><sup>3</sup>)‒H bond of PX is still a main challenge because of the higher bond dissociation energy. Herein, an efficient photocatalytic system for the oxidation of PX to TPA was developed by using tetrabutylammonium decatungstate (TBADT) photocatalyst using atmospheric oxygen as oxidant and 365 nm LED light irradiation. The resulting TPA product was easily separated from the post-reaction solution through simple filtration treatment with a 93.4% yield in CH<sub>3</sub>CN (37.5% 1 mol L<sup>−1</sup> HCl) solvent after 19-h photocatalysis. Given the easy separation of TPA and the excellent recycling stability of TBADT, a continuous-flow photoreactor was successfully designed with promising prospect for potential industrial application. Mechanistic studies elucidated that the presence of HCl additive benefits the structural integrity of [W<sub>10</sub>O<sub>32</sub>]<sup>4−</sup> anions and the transition from excited states [W<sub>10</sub>O<sub>32</sub>]<sup>4−</sup>* to wO active species, leading to enhanced photooxidation performance.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"66 ","pages":"Pages 282-291"},"PeriodicalIF":15.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700289","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 : 2024-11-01DOI: 10.1016/S1872-2067(24)60121-X
Mengran Liu , Canyu Liu , Tianfang Yang , Shixiang Hu , Siyun Li , Shizhe Liu , Yang Liu , Ye Chen , Bingcheng Ge , Shuyan Gao
Transition metal Ni anchored in carbon material represents outstanding 2e− oxygen reduction reaction (ORR) catalytic selectivity, but enhancing the adsorption strength of intermediate *OOH to promote its selectivity remains a major challenge. Herein, the NiX/Ni@NCHS composite catalyst with heteroatom doping (O,S) is modulated by controlling partial pyrolysis strategies on honeycomb-like porous carbon to manipulate the electronic structure of the metal Ni. With the synergistic effect of honeycomb structure and O atom, NiO/Ni@NCHS-700 exhibits an exceptional H2O2 selectivity of above 89.1% across a wide potential range from 0.1 to 0.6 V in an alkaline electrolyte, and an unexpected H2O2 production rate up to 1.47 mol gcat‒1 h‒1@0.2 V, which outperforms most of the state-of-the-art catalyst. Meanwhile, NiS/Ni@NCHS exhibits excellent electrocatalytic performance, with 2e− ORR selectivity of 91.3%, H2O2 yield of 1.85 @0.3 V. Density functional theory simulations and experiments results reveal that the heteroatom doping (O,S) method has been employed to regulate the adsorption strength of Ni atoms with *OOH, and combined with the self-sacrificing template-assisted pyrolysis approach to improve the microstructure of catalysts and optimize the active site. The heteroatom doping method in this work provides significant guidance for promoting 2e− ORR electrocatalysis to produce H2O2.
{"title":"High-efficiency electrochemical H2O2 synthesis by heteroatom-doped NiX/Ni nanocomposites with honeycomb-like porous carbon","authors":"Mengran Liu , Canyu Liu , Tianfang Yang , Shixiang Hu , Siyun Li , Shizhe Liu , Yang Liu , Ye Chen , Bingcheng Ge , Shuyan Gao","doi":"10.1016/S1872-2067(24)60121-X","DOIUrl":"10.1016/S1872-2067(24)60121-X","url":null,"abstract":"<div><div>Transition metal Ni anchored in carbon material represents outstanding 2e<sup>−</sup> oxygen reduction reaction (ORR) catalytic selectivity, but enhancing the adsorption strength of intermediate *OOH to promote its selectivity remains a major challenge. Herein, the NiX/Ni@NCHS composite catalyst with heteroatom doping (O,S) is modulated by controlling partial pyrolysis strategies on honeycomb-like porous carbon to manipulate the electronic structure of the metal Ni. With the synergistic effect of honeycomb structure and O atom, NiO/Ni@NCHS-700 exhibits an exceptional H<sub>2</sub>O<sub>2</sub> selectivity of above 89.1% across a wide potential range from 0.1 to 0.6 V in an alkaline electrolyte, and an unexpected H<sub>2</sub>O<sub>2</sub> production rate up to 1.47 mol g<sub>cat</sub><sup>‒1</sup> h<sup>‒1</sup>@0.2 V, which outperforms most of the state-of-the-art catalyst. Meanwhile, NiS/Ni@NCHS exhibits excellent electrocatalytic performance, with 2e<sup>−</sup> ORR selectivity of 91.3%, H<sub>2</sub>O<sub>2</sub> yield of 1.85 @0.3 V. Density functional theory simulations and experiments results reveal that the heteroatom doping (O,S) method has been employed to regulate the adsorption strength of Ni atoms with *OOH, and combined with the self-sacrificing template-assisted pyrolysis approach to improve the microstructure of catalysts and optimize the active site. The heteroatom doping method in this work provides significant guidance for promoting 2e<sup>−</sup> ORR electrocatalysis to produce H<sub>2</sub>O<sub>2</sub>.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"66 ","pages":"Pages 212-222"},"PeriodicalIF":15.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700246","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 : 2024-11-01DOI: 10.1016/S1872-2067(24)60131-2
Mengna Wang , Qi Wang , Tianfu Liu , Guoxiong Wang
Metal-nitrogen-carbon catalysts (M-N-C) with single-atom active site are highly efficient catalysts for electrochemical CO2 reduction reactions (CO2RR). Abundant M-N-C catalysts have been developed, and the coordinated adjacent nitrogen atoms as first-shell environment have been the focus of research of activity-tuning. However, the effect of second-shell carbon environment around the metal-nitrogen moiety is still unclear. Moreover, it is confusing for the discrepancy between the experimental onset potential of around –0.2 V (vs. reversible hydrogen electrode, RHE, unless otherwise noted) and theoretical predictions of –0.5 V or higher by the widely-used computational hydrogen electrode (CHE) model. Herein, using the explicit solvent model and constant potential method (CPM), the electrochemical interface on Fe-N-C is simulated for CO2RR. It reveals that the *COOH formation is facilitated in water solvent environment, while the CO2 adsorption is potential-dependent. The predicted onset potential of around –0.2 V on Fe-N-C is consistent with experimental results. The sp2 non-hexatomic defects introduced into second-shell carbon environment are significantly influential for the CO2RR. The double five-seven ring (5577) defect is the most active, compared to that with triple five-seven ring (55577) or five-eight ring (58) defects. The highly flexible structure and altered density of states of Fe site induced by 5775 defects are key to CO2 adsorption. This study provides new insights into the role of second-shell carbon environment for effective CO2RR, and underlines the importance of CPM and solvent environment in accurate simulation for electrochemical interface.
{"title":"Unexpected effect of second-shell defect in iron-nitrogen-carbon catalyst for electrochemical CO2 reduction reaction: A DFT study","authors":"Mengna Wang , Qi Wang , Tianfu Liu , Guoxiong Wang","doi":"10.1016/S1872-2067(24)60131-2","DOIUrl":"10.1016/S1872-2067(24)60131-2","url":null,"abstract":"<div><div>Metal-nitrogen-carbon catalysts (M-N-C) with single-atom active site are highly efficient catalysts for electrochemical CO<sub>2</sub> reduction reactions (CO<sub>2</sub>RR). Abundant M-N-C catalysts have been developed, and the coordinated adjacent nitrogen atoms as first-shell environment have been the focus of research of activity-tuning. However, the effect of second-shell carbon environment around the metal-nitrogen moiety is still unclear. Moreover, it is confusing for the discrepancy between the experimental onset potential of around –0.2 V (<em>vs</em>. reversible hydrogen electrode, RHE, unless otherwise noted) and theoretical predictions of –0.5 V or higher by the widely-used computational hydrogen electrode (CHE) model. Herein, using the explicit solvent model and constant potential method (CPM), the electrochemical interface on Fe-N-C is simulated for CO<sub>2</sub>RR. It reveals that the *COOH formation is facilitated in water solvent environment, while the CO<sub>2</sub> adsorption is potential-dependent. The predicted onset potential of around –0.2 V on Fe-N-C is consistent with experimental results. The <em>sp</em><sup>2</sup> non-hexatomic defects introduced into second-shell carbon environment are significantly influential for the CO<sub>2</sub>RR. The double five-seven ring (5577) defect is the most active, compared to that with triple five-seven ring (55577) or five-eight ring (58) defects. The highly flexible structure and altered density of states of Fe site induced by 5775 defects are key to CO<sub>2</sub> adsorption. This study provides new insights into the role of second-shell carbon environment for effective CO<sub>2</sub>RR, and underlines the importance of CPM and solvent environment in accurate simulation for electrochemical interface.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"66 ","pages":"Pages 247-256"},"PeriodicalIF":15.7,"publicationDate":"2024-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142700286","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 : 2024-10-01DOI: 10.1016/S1872-2067(24)60118-X
Huan Liu , Shaoxiong He , Jiafu Qu , Yahui Cai , Xiaogang Yang , Chang Ming Li , Jundie Hu
Dual-channel redox reaction system is advantageous for photocatalytic hydrogen (H2) production when coupled with photoreforming oxidation of waste materials, benefiting both thermodynamically and kinetically. However, existing reviews primarily focus on specific oxidation reactions, such as oxidative organic synthesis and water remediation, often neglecting recent advancements in plastic upgrading, biomass conversion, and H2O2 production, and failing to provide an in-depth discussion of catalytic mechanisms. This review addresses these gaps by offering a comprehensive overview of recent advancements in dual-channel redox reactions for photocatalytic H2-evolution and waste photoreforming. It highlights waste-to-wealth design concepts, examines the challenges, advantages and diverse applications of dual-channel photocatalytic reactions, including photoreforming of biomass, alcohol, amine, plastic waste, organic pollutants, and H2O2 production. Emphasizing improvement strategies and exploration of catalytic mechanisms, it includes advanced in-situ characterization, spin capture experiments, and DFT calculations. By identifying challenges and future directions in this field, this review provides valuable insights for designing innovative dual-channel photocatalytic systems.
{"title":"Dual-channel redox reactions for photocatalytic H2-evolution coupled with photoreforming oxidation of waste materials","authors":"Huan Liu , Shaoxiong He , Jiafu Qu , Yahui Cai , Xiaogang Yang , Chang Ming Li , Jundie Hu","doi":"10.1016/S1872-2067(24)60118-X","DOIUrl":"10.1016/S1872-2067(24)60118-X","url":null,"abstract":"<div><div>Dual-channel redox reaction system is advantageous for photocatalytic hydrogen (H<sub>2</sub>) production when coupled with photoreforming oxidation of waste materials, benefiting both thermodynamically and kinetically. However, existing reviews primarily focus on specific oxidation reactions, such as oxidative organic synthesis and water remediation, often neglecting recent advancements in plastic upgrading, biomass conversion, and H<sub>2</sub>O<sub>2</sub> production, and failing to provide an in-depth discussion of catalytic mechanisms. This review addresses these gaps by offering a comprehensive overview of recent advancements in dual-channel redox reactions for photocatalytic H<sub>2</sub>-evolution and waste photoreforming. It highlights waste-to-wealth design concepts, examines the challenges, advantages and diverse applications of dual-channel photocatalytic reactions, including photoreforming of biomass, alcohol, amine, plastic waste, organic pollutants, and H<sub>2</sub>O<sub>2</sub> production. Emphasizing improvement strategies and exploration of catalytic mechanisms, it includes advanced <em>in-situ</em> characterization, spin capture experiments, and DFT calculations. By identifying challenges and future directions in this field, this review provides valuable insights for designing innovative dual-channel photocatalytic systems.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"65 ","pages":"Pages 1-39"},"PeriodicalIF":15.7,"publicationDate":"2024-10-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142527228","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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