Achieving efficient phosphorus recovery and reuse from wastewater presents formidable challenges. In this study, a synergistic adsorption photocatalysis process was successfully constructed. 0.1Bi-MIL-101-NH showed the maximum phosphorus adsorption performance of 112 mg/g. After phosphorus adsorption, photoelectrochemical measurements confirmed that the photoelectric properties of the 0.1Bi-MIL-101-NH-P sample was improved, and the degradation efficiency of SMX was increased by 20 % within 120 min. Meanwhile, the mineralization rate reached 91 %. The incorporation of Bi significantly enhanced the adsorption energy of the 0.1Bi-MIL-101-NH sample. Notably, the presence of phosphorus on the surface of 0.1Bi-MIL-101-NH-P enhanced the adsorption of water molecules by the material, thereby augmenting the generation of •OH. •O and •OH played dominant roles in the photodegradation of SMX. Finally, the degradation pathways of intermediates were further studied by Density functional theory (DFT) calculations and LC-MS analysis. This study provides a new avenue for phosphorus recovery and organic pollutant degradation.
{"title":"Enhanced photocatalytic performance of 0.1Bi-MIL-101-NH2 after phosphorus adsorption: Synergistic effect of adsorption and photocatalysis","authors":"Yinghao Li, Ying Li, Qinglong Meng, Ke Jing, Jingyi Zhang, Qingyu Guan","doi":"10.1016/j.apcatb.2024.124487","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124487","url":null,"abstract":"Achieving efficient phosphorus recovery and reuse from wastewater presents formidable challenges. In this study, a synergistic adsorption photocatalysis process was successfully constructed. 0.1Bi-MIL-101-NH showed the maximum phosphorus adsorption performance of 112 mg/g. After phosphorus adsorption, photoelectrochemical measurements confirmed that the photoelectric properties of the 0.1Bi-MIL-101-NH-P sample was improved, and the degradation efficiency of SMX was increased by 20 % within 120 min. Meanwhile, the mineralization rate reached 91 %. The incorporation of Bi significantly enhanced the adsorption energy of the 0.1Bi-MIL-101-NH sample. Notably, the presence of phosphorus on the surface of 0.1Bi-MIL-101-NH-P enhanced the adsorption of water molecules by the material, thereby augmenting the generation of •OH. •O and •OH played dominant roles in the photodegradation of SMX. Finally, the degradation pathways of intermediates were further studied by Density functional theory (DFT) calculations and LC-MS analysis. This study provides a new avenue for phosphorus recovery and organic pollutant degradation.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943246","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}
Herein, the TiO electrode was combined for the first time with various oxidants to generate reactive oxygen species for the removal of different organic pollutants in an electrochemical oxidation (EO) system. The removal efficiency of organic pollutants, reaction mechanism, and degradation pathway were evaluated by electrochemical tests, reaction kinetics, electron paramagnetic resonance, quantum chemical, and density functional theory calculations. As a result, nearly 100 % removal efficiency of sulfamethoxazole (SMX) was achieved within 12 min with a high kinetic rate constant of 0.259 min, and the kinetic rate constant was strongly dependent on the electrostatic potential. The O2 site on the peroxymonosulfate (PMS) molecule dominated the radical generation for the removal of SMX via the radical and non−radical process. This current study offers a novel approach toward the electrochemical activation of PMS in the elimination and degradation of various organic pollutant from wastewater.
{"title":"Unraveling degradation mechanism and reaction efficacy of sulfamethoxazole via reactive oxygen species dominated radical process","authors":"Hongguo Zhang, Peitong Cen, Jiashuo Li, Chenxi Li, Jiayu Song, Qiong Wu, Wei Han, Lei Huang, Jia Yan, Shaoqi Zhou, Ce-Hui Mo, Meng Li","doi":"10.1016/j.apcatb.2024.124484","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124484","url":null,"abstract":"Herein, the TiO electrode was combined for the first time with various oxidants to generate reactive oxygen species for the removal of different organic pollutants in an electrochemical oxidation (EO) system. The removal efficiency of organic pollutants, reaction mechanism, and degradation pathway were evaluated by electrochemical tests, reaction kinetics, electron paramagnetic resonance, quantum chemical, and density functional theory calculations. As a result, nearly 100 % removal efficiency of sulfamethoxazole (SMX) was achieved within 12 min with a high kinetic rate constant of 0.259 min, and the kinetic rate constant was strongly dependent on the electrostatic potential. The O2 site on the peroxymonosulfate (PMS) molecule dominated the radical generation for the removal of SMX via the radical and non−radical process. This current study offers a novel approach toward the electrochemical activation of PMS in the elimination and degradation of various organic pollutant from wastewater.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943247","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}
The electrochemical CO reduction reaction conducted presents a promising strategy to facilitate the artificial carbon cycle. Unfortunately, the efficiency of eCORR-to-C remains below the level required for large-scale implementation due to complex multi-electron transfer and sluggish carbon-carbon coupling. Herein, we constructed asymmetric Zn-O-Cu sites on 2.12 %Zn/CuO, which achieving a maximum C product FE of 78.77 ± 1.90 % and a high current density of 408.3 mA cm. Experimental and theoretical studies reveal that the O-bridged asymmetric Zn-O-Cu sites exhibit enhanced electron transfer, which plays a pivotal role in improving the coverage of *CO and adjusting the adsorption strength of the *CO. The optimal adsorption capacity of the *CO on 2.12 %Zn/CuO facilitated the subsequent hydrogenation reaction to enhance the conversion of *CO to *COH. Consequently, the asymmetric Zn-O-Cu sites proved to be more thermodynamically favorable for the asymmetric coupling between *CO and *COH, which is conducive to the production of C products.
电化学一氧化碳还原反应为促进人工碳循环提供了一种前景广阔的策略。遗憾的是，由于复杂的多电子转移和迟缓的碳碳耦合，eCORR-to-C 的效率仍然低于大规模实施所需的水平。在此，我们在 2.12 %Zn/CuO 上构建了不对称 Zn-O-Cu 位点，实现了最大 78.77 ± 1.90 % 的碳产物 FE 和 408.3 mA cm 的高电流密度。实验和理论研究表明，O 桥非对称 Zn-O-Cu 位点具有增强的电子传递能力，在提高*CO 的覆盖率和调节*CO 的吸附强度方面起着关键作用。*CO 在 2.12 %Zn/CuO 上的最佳吸附能力促进了随后的氢化反应，提高了 *CO 向 *COH 的转化。因此，不对称的 Zn-O-Cu 位点被证明在热力学上更有利于 *CO 和 *COH 之间的不对称偶联，从而有利于 C 产物的生成。
{"title":"Enhanced CO2 electroreduction to C2+ production on asymmetric Zn-O-Cu sites via tuning of *CO intermediate adsorption","authors":"Zijian Fang, Weiwei Guo, Guixian Xie, Guoliang Mei, Yanling Zhai, Zhijun Zhu, Xiaoquan Lu, Jianguo Tang","doi":"10.1016/j.apcatb.2024.124473","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124473","url":null,"abstract":"The electrochemical CO reduction reaction conducted presents a promising strategy to facilitate the artificial carbon cycle. Unfortunately, the efficiency of eCORR-to-C remains below the level required for large-scale implementation due to complex multi-electron transfer and sluggish carbon-carbon coupling. Herein, we constructed asymmetric Zn-O-Cu sites on 2.12 %Zn/CuO, which achieving a maximum C product FE of 78.77 ± 1.90 % and a high current density of 408.3 mA cm. Experimental and theoretical studies reveal that the O-bridged asymmetric Zn-O-Cu sites exhibit enhanced electron transfer, which plays a pivotal role in improving the coverage of *CO and adjusting the adsorption strength of the *CO. The optimal adsorption capacity of the *CO on 2.12 %Zn/CuO facilitated the subsequent hydrogenation reaction to enhance the conversion of *CO to *COH. Consequently, the asymmetric Zn-O-Cu sites proved to be more thermodynamically favorable for the asymmetric coupling between *CO and *COH, which is conducive to the production of C products.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943249","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 : 2024-08-08DOI: 10.1016/j.apcatb.2024.124471
Xianjing Liu, Ying Wang, John Crittenden, Qi Su, Huatao Mo
The inhibition of oxidation efficiency and the formation of toxic chlorinated organic byproducts owing to Cl still represent a significant threat to the treatment of high chloride organic wastewater using advanced oxidation processes. This study explores new pathways for utilizing Cl to promote the formation of Fe(Ⅳ)=O by single atom Fe-CNs catalysts under peroxymonosulfate (PMS) system, which significantly increases sulfamethoxazole (SMX) degradation rate constant by 2.97 times, enhances PMS utilization efficiency (reducing by 92 % PMS consumption) and simultaneously avoids the formation of chlorinated organic byproducts. Experiments and theoretical calculation revealed that the in-situ generated HClO (generated via the reaction of PMS and Cl) more easily reacts with Fe–pyridinic N active sites of Fe-CNs catalysts to generate Fe(Ⅳ)=O through a lower-energy-barrier pathway, rather than directly oxidates pollutants. This study provides an approach to utilize omnipresent Cl achieving high efficiency, high selectivity, low PMS consumption and harmless treatment for chloride-containing organic wastewaters.
{"title":"Enhanced treatment of high chloride organic wastewater under lower peroxymonosulfate consumption: A pathway for the formation of Fe(IV)=O excited by chloride ions","authors":"Xianjing Liu, Ying Wang, John Crittenden, Qi Su, Huatao Mo","doi":"10.1016/j.apcatb.2024.124471","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124471","url":null,"abstract":"The inhibition of oxidation efficiency and the formation of toxic chlorinated organic byproducts owing to Cl still represent a significant threat to the treatment of high chloride organic wastewater using advanced oxidation processes. This study explores new pathways for utilizing Cl to promote the formation of Fe(Ⅳ)=O by single atom Fe-CNs catalysts under peroxymonosulfate (PMS) system, which significantly increases sulfamethoxazole (SMX) degradation rate constant by 2.97 times, enhances PMS utilization efficiency (reducing by 92 % PMS consumption) and simultaneously avoids the formation of chlorinated organic byproducts. Experiments and theoretical calculation revealed that the in-situ generated HClO (generated via the reaction of PMS and Cl) more easily reacts with Fe–pyridinic N active sites of Fe-CNs catalysts to generate Fe(Ⅳ)=O through a lower-energy-barrier pathway, rather than directly oxidates pollutants. This study provides an approach to utilize omnipresent Cl achieving high efficiency, high selectivity, low PMS consumption and harmless treatment for chloride-containing organic wastewaters.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943250","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 : 2024-08-08DOI: 10.1016/j.apcatb.2024.124488
Jingzhi Wang, Mei Li, Youlin Wu, Nini Zhao, Zhiliang Jin
The large amount of organic wastewater generated by the coal chemical industry requires multiple processes to remove harmful substances, which is costly. Based on this, palladium-modified GDY (Pd-GDY) was prepared for the first time, using acetylene gas generated from carbide slag as a precursor. And grow CdS on its surface to form Pd-GDY/CdS heterostructure material. The photocatalytic performance in coal chemical wastewater can reach 7.35 μmol·g·h. Meanwhile, in the industrial hydrogen production experiment on a square meter scale, the hydrogen production rate reached 3.42 mmol·h. Density functional theory (DFT) calculations indicate that the excellent hydrogen evolution activity is attributed to the regulation of the d band center by Pd-GDY. More antibonding energy bands are below the Fermi level, filled with electrons, reducing bond stability and adsorption strength, resulting in a decrease in hydrogen adsorption free energy. Overall, this work provides new insights into the synthesis of novel graphdiyne and its application in wastewater and industrial hydrogen production based on regulating d band center in heterogeneous catalytic systems.
煤化工行业产生的大量有机废水需要通过多种工艺去除有害物质，成本高昂。在此基础上，利用电石渣产生的乙炔气作为前驱体，首次制备出了钯改性 GDY（Pd-GDY）。并在其表面生长 CdS，形成 Pd-GDY/CdS 异质结构材料。在煤化工废水中的光催化性能可达 7.35 μmol-g-h。同时，在一平方米规模的工业制氢实验中，制氢率达到了 3.42 mmol-h。密度泛函理论（DFT）计算表明，出色的氢气进化活性归功于 Pd-GDY 对 d 能带中心的调节。更多的反键能带位于费米级以下，充满了电子，降低了键的稳定性和吸附强度，导致氢吸附自由能降低。总之，这项工作为新型石墨二炔的合成及其在废水和工业制氢中的应用提供了新的见解，其基础是调节异相催化体系中的 d 带中心。
{"title":"A novel palladium decorated graphdiyne regulating d band center enhanced the ability of square meter scale and coal chemical wastewater for efficient hydrogen production","authors":"Jingzhi Wang, Mei Li, Youlin Wu, Nini Zhao, Zhiliang Jin","doi":"10.1016/j.apcatb.2024.124488","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124488","url":null,"abstract":"The large amount of organic wastewater generated by the coal chemical industry requires multiple processes to remove harmful substances, which is costly. Based on this, palladium-modified GDY (Pd-GDY) was prepared for the first time, using acetylene gas generated from carbide slag as a precursor. And grow CdS on its surface to form Pd-GDY/CdS heterostructure material. The photocatalytic performance in coal chemical wastewater can reach 7.35 μmol·g·h. Meanwhile, in the industrial hydrogen production experiment on a square meter scale, the hydrogen production rate reached 3.42 mmol·h. Density functional theory (DFT) calculations indicate that the excellent hydrogen evolution activity is attributed to the regulation of the d band center by Pd-GDY. More antibonding energy bands are below the Fermi level, filled with electrons, reducing bond stability and adsorption strength, resulting in a decrease in hydrogen adsorption free energy. Overall, this work provides new insights into the synthesis of novel graphdiyne and its application in wastewater and industrial hydrogen production based on regulating d band center in heterogeneous catalytic systems.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141969302","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 : 2024-08-06DOI: 10.1016/j.apcatb.2024.124460
Corinna Fauth, Ali M. Abdel-Mageed, R.Jürgen Behm
Continuing a comprehensive study of the reduction of CO over supported Ru catalysts, we explored the interaction of CO with Ru/γ-AlO by TAP reactor measurements, focusing on dynamic aspects in adsorption/desorption, reaction and oxygen exchange processes. Pulse shape analysis in H/CO multipulse sequences provides information on the interaction of reactant/product species with the catalyst. The measurements provide information on the dynamic build-up of reaction intermediates and more stable adspecies during pulsing, and its relation to CH formation. Facile oxygen exchange between CO and catalyst, followed by isotope labeling experiments, is quantitatively reconciled in a simple model, relating the ratio between different CO isotopologues to the O:O ratio in the total exchangeable oxygen on the surface and in the CO pulse. The results provide detailed insight into various aspects of the interaction between CO and Ru/AlO catalysts important for a mechanistic understanding of various catalytic reactions involving CO.
在继续对支撑型 Ru 催化剂还原 CO 的综合研究的同时，我们通过 TAP 反应器测量探究了 CO 与 Ru/γ-AlO 的相互作用，重点关注吸附/解吸、反应和氧交换过程的动态方面。H/CO 多脉冲序列中的脉冲形状分析提供了反应物/产物物种与催化剂相互作用的信息。测量结果提供了脉冲过程中反应中间产物和更稳定吸附物种的动态积累及其与 CH 形成之间关系的信息。一氧化碳与催化剂之间的便捷氧交换，以及随后的同位素标记实验，都可以通过一个简单的模型进行定量调节，该模型将不同一氧化碳同位素之间的比率与表面和一氧化碳脉冲中总可交换氧的 O:O 比率联系起来。研究结果详细揭示了 CO 与 Ru/AlO 催化剂之间相互作用的各个方面，对于从机理上理解涉及 CO 的各种催化反应非常重要。
{"title":"Temporal analysis of products (TAP) reactor study of the dynamics of CO2 interaction with a Ru/γ-Al2O3 supported catalyst II: Interaction strength, formation of intermediates and oxygen exchange","authors":"Corinna Fauth, Ali M. Abdel-Mageed, R.Jürgen Behm","doi":"10.1016/j.apcatb.2024.124460","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124460","url":null,"abstract":"Continuing a comprehensive study of the reduction of CO over supported Ru catalysts, we explored the interaction of CO with Ru/γ-AlO by TAP reactor measurements, focusing on dynamic aspects in adsorption/desorption, reaction and oxygen exchange processes. Pulse shape analysis in H/CO multipulse sequences provides information on the interaction of reactant/product species with the catalyst. The measurements provide information on the dynamic build-up of reaction intermediates and more stable adspecies during pulsing, and its relation to CH formation. Facile oxygen exchange between CO and catalyst, followed by isotope labeling experiments, is quantitatively reconciled in a simple model, relating the ratio between different CO isotopologues to the O:O ratio in the total exchangeable oxygen on the surface and in the CO pulse. The results provide detailed insight into various aspects of the interaction between CO and Ru/AlO catalysts important for a mechanistic understanding of various catalytic reactions involving CO.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943254","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 : 2024-08-06DOI: 10.1016/j.apcatb.2024.124466
Siyu Qiang, Hualei Liu, Fan Wu, Shuyu Liu, Sijuan Zeng, Yihe Yin, Fei Wang, Jianyong Yu, Yi-Tao Liu, Bin Ding
Suppressing parasitic hydrogen evolution reaction (HER) remains a dilemma in developing aqueous electrochemical nitrogen reduction reaction (NRR). Nevertheless, previous studies have revealed the significant challenge of relying solely on electrocatalyst design to pursue selective NRR. Herein, we present a ‘Trio’ strategy to harmonize electronic structures of electrocatalysts, properties of interfaces, and configurations of microenvironments, thereby governing the intricate proton behaviors throughout the reaction, to suppress HER while boosting NRR. As proof-of-concept demonstration, the first designed amorphous InO-based nanofiber electrocatalyst, with optimized electronic state by oxygen vacancy and anchoring Mo species, is in conjunction with low-surface-energy monolayer interface and molecular-crowding microenvironment. Such rational synergy creates an advantageous catalytic configuration with decelerated proton diffusion and restricted proton transfer to active sites, thus achieving NH yield of 59.72 μg h mg and a FE of 30.60 %. We expect these findings will inspire “collaborative combat” strategies and desirable systems of NRR in the future.
抑制寄生氢进化反应（HER）仍然是开发水电化学氮还原反应（NRR）的一个难题。然而，以往的研究表明，仅仅依靠电催化剂设计来实现选择性氮还原反应是一项重大挑战。在此，我们提出了一种 "三重奏 "策略，即协调电催化剂的电子结构、界面特性和微环境配置，从而控制整个反应过程中错综复杂的质子行为，在抑制 HER 的同时提高 NRR。作为概念验证，首次设计的非晶 InO 基纳米纤维电催化剂通过氧空位和锚定 Mo 物种优化了电子状态，并与低表面能单层界面和分子拥挤的微环境相结合。这种合理的协同作用创造了一种有利的催化构型，质子扩散速度减慢，质子向活性位点的转移受到限制，从而实现了 59.72 μg h mg 的 NH 产率和 30.60 % 的 FE。我们期待这些发现将在未来激发 "协同作战 "战略和理想的 NRR 系统。
{"title":"Trio strategy of harmonizing electronic structure, interface, and microenvironment on amorphous indium oxide nanofiber for selective electrochemical ammonia synthesis","authors":"Siyu Qiang, Hualei Liu, Fan Wu, Shuyu Liu, Sijuan Zeng, Yihe Yin, Fei Wang, Jianyong Yu, Yi-Tao Liu, Bin Ding","doi":"10.1016/j.apcatb.2024.124466","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124466","url":null,"abstract":"Suppressing parasitic hydrogen evolution reaction (HER) remains a dilemma in developing aqueous electrochemical nitrogen reduction reaction (NRR). Nevertheless, previous studies have revealed the significant challenge of relying solely on electrocatalyst design to pursue selective NRR. Herein, we present a ‘Trio’ strategy to harmonize electronic structures of electrocatalysts, properties of interfaces, and configurations of microenvironments, thereby governing the intricate proton behaviors throughout the reaction, to suppress HER while boosting NRR. As proof-of-concept demonstration, the first designed amorphous InO-based nanofiber electrocatalyst, with optimized electronic state by oxygen vacancy and anchoring Mo species, is in conjunction with low-surface-energy monolayer interface and molecular-crowding microenvironment. Such rational synergy creates an advantageous catalytic configuration with decelerated proton diffusion and restricted proton transfer to active sites, thus achieving NH yield of 59.72 μg h mg and a FE of 30.60 %. We expect these findings will inspire “collaborative combat” strategies and desirable systems of NRR in the future.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943253","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}
Light-driven selective organic synthesis presents a promising means to sustainable production of value-added fine chemicals. Nonetheless, the photocatalytic efficiency is obstructed by low charge transfer efficiency and few uncoordinated electrons. Herein, hollow multi-shelled PbBiOBr nanospheres with atomically thin shells and richly local polarization sites were initially synthesized to effectively tackle these issues. The ultrathin hollow multi-shelled geometry facilitates charge separation and offers spatially distributed catalytic sites for redox reactions. The local polarization induced by oxygen vacancies can afford abundant coordination-unsaturated sites, effectively facilitate the activation of O and benzyl alcohol, significantly lower free energy barrier through the formation of stable Pb−O−Bi intermediate. Consequently, the richly polarized PbBiOBr hollow multi-shelled nanospheres exhibit excellent catalytic activity (96 % conversion and 99 % selectivity) and superior adaptability for selective oxidation of aromatic alcohols to aldehydes. The results can motivate the study on hollow multi-shelled geometry with local polarization for fine chemicals photosynthesis.
{"title":"Regulating local polarization in hollow multi-shelled nanospheres for efficient atomic site activation towards selective aerobic oxidation of aromatic alcohols","authors":"Danjun Mao, Tong Li, Xiufeng Lu, Tao Guo, Huan He, Heyun Fu, Zheyang Liu, Shourong Zheng, Cheng Sun, Zhaoyi Xu, Zhifeng Jiang, Xiaolei Qu","doi":"10.1016/j.apcatb.2024.124481","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124481","url":null,"abstract":"Light-driven selective organic synthesis presents a promising means to sustainable production of value-added fine chemicals. Nonetheless, the photocatalytic efficiency is obstructed by low charge transfer efficiency and few uncoordinated electrons. Herein, hollow multi-shelled PbBiOBr nanospheres with atomically thin shells and richly local polarization sites were initially synthesized to effectively tackle these issues. The ultrathin hollow multi-shelled geometry facilitates charge separation and offers spatially distributed catalytic sites for redox reactions. The local polarization induced by oxygen vacancies can afford abundant coordination-unsaturated sites, effectively facilitate the activation of O and benzyl alcohol, significantly lower free energy barrier through the formation of stable Pb−O−Bi intermediate. Consequently, the richly polarized PbBiOBr hollow multi-shelled nanospheres exhibit excellent catalytic activity (96 % conversion and 99 % selectivity) and superior adaptability for selective oxidation of aromatic alcohols to aldehydes. The results can motivate the study on hollow multi-shelled geometry with local polarization for fine chemicals photosynthesis.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943251","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}
The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key performance-limiting step of rechargeable zinc-air batteries. Developing a reliable strategy to optimize the activity of Co occupied the tetrahedral site (Co) is crucial for enhancing electrocatalytic performance and still needs further elaborate elucidation. Here, Mo dopants were used as electron donors to construct low-valence Co sites in cobalt phosphide, resulting in downshifted -band centers and strengthened hybridization between Co 3 and P 3 orbitals. The negative charges are easier to accumulate on three antibonding orbitals of Co, promoting the desorption of oxygen intermediates, as evidenced using density functional theory calculations and spectroscopic investigations. The optimal catalyst delivers impressive ORR and OER performance, in terms of half-wave potential of 0.84 V for ORR and overpotential of 247 mV for OER. In general, this work opens a new opportunity to rationally regulate electronic structure of Co sites introducing an electron donor, as well as provides guidance for exploring electronic descriptors of tetrahedral sites.
氧还原反应（ORR）和氧进化反应（OER）是限制可充电锌-空气电池性能的关键步骤。开发一种可靠的策略来优化占据四面体位点（Co）的 Co 的活性，对于提高电催化性能至关重要，但仍需进一步详细阐明。在这里，掺杂钼作为电子供体在磷化钴中构建了低电价钴位点，从而导致带中心下移，并加强了钴 3 和 P 3 轨道之间的杂化。密度泛函理论计算和光谱研究证明，负电荷更容易聚集在 Co 的三个反键轨道上，从而促进氧中间产物的解吸。最佳催化剂具有令人印象深刻的 ORR 和 OER 性能，ORR 的半波电位为 0.84 V，OER 的过电位为 247 mV。总之，这项工作为合理调节引入电子供体的 Co 位点的电子结构提供了新的机遇，并为探索四面体位点的电子描述符提供了指导。
{"title":"Constructing electron-enriched Co tetrahedral sites to promote oxygen electrocatalysis in rechargeable zinc-air batteries","authors":"Jingrui Han, Jieshu Zhou, Wei Song, Hao Zhang, Ziyun Wang, Kangning Liu, Yong Li, Weijun Zhu, Xuhui Sun, Hongyan Liang","doi":"10.1016/j.apcatb.2024.124468","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124468","url":null,"abstract":"The oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) is a key performance-limiting step of rechargeable zinc-air batteries. Developing a reliable strategy to optimize the activity of Co occupied the tetrahedral site (Co) is crucial for enhancing electrocatalytic performance and still needs further elaborate elucidation. Here, Mo dopants were used as electron donors to construct low-valence Co sites in cobalt phosphide, resulting in downshifted -band centers and strengthened hybridization between Co 3 and P 3 orbitals. The negative charges are easier to accumulate on three antibonding orbitals of Co, promoting the desorption of oxygen intermediates, as evidenced using density functional theory calculations and spectroscopic investigations. The optimal catalyst delivers impressive ORR and OER performance, in terms of half-wave potential of 0.84 V for ORR and overpotential of 247 mV for OER. In general, this work opens a new opportunity to rationally regulate electronic structure of Co sites introducing an electron donor, as well as provides guidance for exploring electronic descriptors of tetrahedral sites.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943014","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 : 2024-08-02DOI: 10.1016/j.apcatb.2024.124463
Tian Tian, Peixin Zhu, Chun He, Ya Xiong, Jingyun Fang, Shuanghong Tian
As initial and important reactive species, surface O complexes are rarely investigated in catalytic ozonation, which might be one cause of dispute in mechanistic understanding. Herein, In-situ DRIFTS and premixing-standing experiments confirmed the generation of long-lived Mn-O* complexes upon O adsorption on surface Lewis acid sites of α-MnO. In α-MnO/O system, the oxidation rate of various pollutants showed a good linear correlation with their redox potentials, as well as the energy gap between the pollutants and Mn-O* complexes. Joint catalytic mechanism experiments and density functional theory calculations revealed that the oxidation of pollutants was boosted mainly because there was fast nonradical intermolecular electron transfer from the HOMO of pollutants to the LUMO of Mn-O* complexes. This study illustrates the significance of surface Mn-O* complex in catalytic ozonation and discloses an efficient nonradical catalytic ozonation process that is resistant to pH fluctuation and matrix interference.
作为最初的重要反应物，表面 O 复合物在催化臭氧过程中很少被研究，这可能是机理认识上存在争议的原因之一。在此，原位 DRIFTS 和预混立实验证实了 α-MnO 表面路易斯酸位点吸附 O 后生成长寿命 Mn-O* 复合物。在 α-MnO/O 体系中，各种污染物的氧化率与其氧化还原电位以及污染物与 Mn-O* 复合物之间的能隙呈良好的线性关系。联合催化机理实验和密度泛函理论计算表明，污染物的氧化率之所以得到提高，主要是因为污染物的 HOMO 与 Mn-O* 复合物的 LUMO 之间存在快速的非辐射分子间电子转移。这项研究说明了表面 Mn-O* 复合物在催化臭氧氧化过程中的重要作用，并揭示了一种高效的非辐射催化臭氧氧化过程，该过程不受 pH 值波动和基质干扰的影响。
{"title":"Surface Mn-O3* complex-mediated nonradical electron transfer for boosting catalytic ozonation of organic pollutants","authors":"Tian Tian, Peixin Zhu, Chun He, Ya Xiong, Jingyun Fang, Shuanghong Tian","doi":"10.1016/j.apcatb.2024.124463","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124463","url":null,"abstract":"As initial and important reactive species, surface O complexes are rarely investigated in catalytic ozonation, which might be one cause of dispute in mechanistic understanding. Herein, In-situ DRIFTS and premixing-standing experiments confirmed the generation of long-lived Mn-O* complexes upon O adsorption on surface Lewis acid sites of α-MnO. In α-MnO/O system, the oxidation rate of various pollutants showed a good linear correlation with their redox potentials, as well as the energy gap between the pollutants and Mn-O* complexes. Joint catalytic mechanism experiments and density functional theory calculations revealed that the oxidation of pollutants was boosted mainly because there was fast nonradical intermolecular electron transfer from the HOMO of pollutants to the LUMO of Mn-O* complexes. This study illustrates the significance of surface Mn-O* complex in catalytic ozonation and discloses an efficient nonradical catalytic ozonation process that is resistant to pH fluctuation and matrix interference.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141943024","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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