Yu Nie , Yanfang Li , Chao An , Xin Tan , Zhuofeng Hu , Jinhua Ye , Tao Yu
{"title":"Promoted selectivity of photocatalytic CO2 reduction to C2H4 via hybrid CuxCoSy possessing dual unsaturated sites","authors":"Yu Nie , Yanfang Li , Chao An , Xin Tan , Zhuofeng Hu , Jinhua Ye , Tao Yu","doi":"10.1016/j.apcatb.2024.123704","DOIUrl":"10.1016/j.apcatb.2024.123704","url":null,"abstract":"<div><p>Ethylene production by CO<sub>2</sub> reduction is sluggish because the repulsive dipole-dipole interaction and 12 proton-coupled electron-transfer steps consecutively. Amorphous structured photocatalysts possess few grain boundaries and abundant unsaturated sites, accelerating the reaction efficiency from the angle of dynamics and thermodynamics, which still not yet be used in PCR to C<sub>2</sub> products currently. Herein, an amorphous Cu<sub>x</sub>CoS<sub>y</sub> composed of the minority crystalline CuCo<sub>2</sub>S<sub>4</sub> is fabricated to realize an excellent C<sub>2</sub>H<sub>4</sub> selectivity in terms of R<sub>electron</sub> (94.9%). Unsaturated Co and S play the key roles in the improved efficiency of C<sub>2</sub>H<sub>4</sub> generation. C-C coupling is achieved via shortening Co-S bonds distance, and *CO-*CO coupling barrier is decreased by more electrons accumulated on unsaturated S. Water is adsorbed on Co adjacent to S and provide protons for *COCO to form *CH<sub>2</sub> = C. This work paves a new way for broadening the efficient of C<sub>2</sub>H<sub>4</sub> photocatalytic evolution using amorphous photocatalyst.</p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"345 ","pages":"Article 123704"},"PeriodicalIF":22.1,"publicationDate":"2024-01-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139410418","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}
{"title":"Synergistic Regulation of Charge State and Electron-donating Ability via Heterojunctions Design for Fixation of Electronegative Greenhouse F-gases","authors":"Xiang Meng, Boxu Dong, Liang Zhao, Wenhui Zhou, Xinhao Li, Jiantao Zai, Xuefeng Qian","doi":"10.1016/j.apcatb.2024.123709","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.123709","url":null,"abstract":"<p>The net-zero greenhouse gas emission has now become a global strategy. In this context, electronegative fluorinated-gases such as sulfur hexafluoride (SF<sub>6</sub>) and hydrofluorocarbon, have become important emission reduction objects due to their strong global warming potential. In this work, the MnOx@Mn/SiC heterojunction was rationally designed and prepared. Because of the high electron coupling, the positively charged active-site MnOx@Mn (δ<sup>+</sup>) not only promotes the adsorption of SF<sub>6</sub> but also acts as a donor to transport electrons to SF<sub>6</sub>, so that the adsorption and activation of SF<sub>6</sub> are unified in one active site. Therefore, MnOx@Mn/SiC can effectively degrade SF<sub>6</sub> above 450℃, and the degradation amount for 12 vol.% SF<sub>6</sub> can reach 523.8<!-- --> <!-- -->mL<!-- --> <!-- -->g<sup>-1</sup> at 600℃. Furthermore, it also has good degradation performance on hydrofluorocarbons (R-22 and R-410A) even at 100℃. Given the cheap and easy scale-up synthesis, MnOx@Mn/SiC has the potential to reduce the emission of multiple fluorinated-gases in practical applications.</p>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"18 1","pages":""},"PeriodicalIF":22.1,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139410032","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}
{"title":"Promoted electro-oxidation kinetics in chromium-doped α‑Ni(OH)2 nanosheets for efficient selective conversion of methanol to formate","authors":"Yu Fan, Xu Yang, Enhui Wei, Yuan Dong, Hongtao Gao, Xiliang Luo, Wenlong Yang","doi":"10.1016/j.apcatb.2024.123716","DOIUrl":"10.1016/j.apcatb.2024.123716","url":null,"abstract":"<div><p><span>Owing to the elusive pathways of methanol oxidation reaction (MOR) and the lack of applicable catalysts, the selective electro-oxidation of methanol to formate remains a challenging topic. Herein, we present a chromium-doping strategy to promote the MOR performance of α-Ni(OH)</span><sub>2</sub><span> nanosheets with a high selectivity towards formate generation. Taking chromium-doped α-Ni(OH)</span><sub>2</sub> nanosheets as an example, we further highlight the role of doping atoms in MOR by combining theoretical calculations with experimental measurements. It reveals that chromium doping can not only enhance the conductivity of α-Ni(OH)<sub>2</sub> nanosheets, but also endow the catalyst with optimized kinetics for electroactive NiOOH formation and methanol absorption, thus resulting in a remarkable MOR current density of 141 mA cm<sup>−2</sup> at 0.50 V vs. Ag/AgCl with a faradaic efficiency of 92.1% for formate. Furthermore, in situ infrared spectroscopy demonstrates that methanol is selectively oxidized to formate without further oxidation to CO<sub>2</sub> over chromium-doped α‑Ni(OH)<sub>2</sub> nanosheets in alkaline media.</p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"345 ","pages":"Article 123716"},"PeriodicalIF":22.1,"publicationDate":"2024-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139410148","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}
Wentao Bao , Ying Tang , Jie Yu , Wenxia Yan , Chenxu Wang , Yangyang Li , Zhimou Wang , Jinfeng Yang , Lili Zhang , Feng Yu
{"title":"Si-doped ZnAl-LDH nanosheets by layer-engineering for efficient photoelectrocatalytic water splitting","authors":"Wentao Bao , Ying Tang , Jie Yu , Wenxia Yan , Chenxu Wang , Yangyang Li , Zhimou Wang , Jinfeng Yang , Lili Zhang , Feng Yu","doi":"10.1016/j.apcatb.2024.123706","DOIUrl":"10.1016/j.apcatb.2024.123706","url":null,"abstract":"<div><p><span>A highly efficient Si-doped ZnAl-LDH (denoted as Si-ZnAl-LDH nanosheet) catalyst that is derived from large-area chemical exfoliation for photoelectrocatalytic water splitting. The formation of amorphous Si-ZnAl-LDH nanosheets through chemical exfoliation or layer engineering leads to much more accessible surfaces that originally are not accessible in highly crystalline ZnAl-LDH sheets. The incorporation of Si to highly exfoliated ZnAl-LDH nanosheets generates more oxygen vacancies, increases the number of active sites, redistributes the local charge density of the active centers and effectively suppresses the recombination of the generated electron-hole pairs. Specifically, the overpotential of HER and OER for Si-ZnAl-LDH nanosheet is 108 mV and 260 mV, respectively, at current density of 10 mA cm</span><sup>−2</sup> under light-assisted conditions. Total applied voltage is 1.673 V for water splitting in a full cell. This work provides a novel chemical exfoliation or layer-engineering strategy for the synthesis of scalable and cost-effective LDH nanosheets with efficient photoelectric response.</p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"346 ","pages":"Article 123706"},"PeriodicalIF":22.1,"publicationDate":"2024-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139396703","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}
{"title":"Unbiased photoelectrochemical carbon dioxide reduction shaping the future of solar fuels","authors":"Haijiao Lu, Lianzhou Wang","doi":"10.1016/j.apcatb.2024.123707","DOIUrl":"10.1016/j.apcatb.2024.123707","url":null,"abstract":"<div><p><span>As atmospheric carbon dioxide (CO</span><sub>2</sub>) levels surge due to human activities, addressing this global crisis is paramount. This article delves into the realm of photoelectrochemical (PEC) CO<sub>2</sub> reduction, a promising solution that combines solar energy conversion and electrochemical processes to transform CO<sub>2</sub> into clean energy fuels. The primary focus of this article lies in the cutting-edge unbiased PEC tandem configurations, specifically reviewing recent breakthroughs in coupling PEC CO<sub>2</sub><span> reduction with the oxygen evolution reaction through water oxidation. By consolidating the latest insights and knowledge, this comprehensive review guides readers through the evolving landscape of advanced PEC technologies. Furthermore, it provides insights into prospective developments in this evolving field, shedding light on the paths toward sustainable energy solutions and climate mitigation.</span></p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"345 ","pages":"Article 123707"},"PeriodicalIF":22.1,"publicationDate":"2024-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139376213","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}
Shaoqiang Li , Yi-lei Li , Hui-min Bai , Dong-ying Zhou , Ying Liu , Rui-hong Liu , Bao-hang Han , Xinying Liu , Fa-tang Li
{"title":"Penta-coordinated aluminum species: Anchoring Au single atoms for photocatalytic CO2 reduction","authors":"Shaoqiang Li , Yi-lei Li , Hui-min Bai , Dong-ying Zhou , Ying Liu , Rui-hong Liu , Bao-hang Han , Xinying Liu , Fa-tang Li","doi":"10.1016/j.apcatb.2024.123703","DOIUrl":"10.1016/j.apcatb.2024.123703","url":null,"abstract":"<div><p>Searching substrate materials having inherent photocatalytic activity and interaction with single atoms remains challenge. Herein, amorphous Al<sub>2</sub>O<sub>3</sub> containing penta-coordinated aluminum (Al<sup>V</sup>) species is synthesized using the solvothermal method and the Au single atom is anchored by Al<sup>V</sup> via the self-reduction strategy. The Al-O bond energy is weakened by introducing amorphous components, which benefits the release of oxygen atoms and the resultant change of Al coordination environment to a Al<sup>V</sup> species. The electron transfer between Al<sup>V</sup> and Au stabilizes the Au single atom. The introduction of the Au single atom occupying the position of O vacancy and anchored by Al<sup>V</sup> strengthened the chemical absorption abilities for CO<sub>2,</sub> lowered the energy barrier of CO generation and promoted the charge separation efficiency. The CO generation rate of the Au single atom anchored obtains extraordinary promotion in comparison with pristine Al<sub>2</sub>O<sub>3</sub>, resulting in an approximately 6-fold enhancement and 98% product CO selectivity.</p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"345 ","pages":"Article 123703"},"PeriodicalIF":22.1,"publicationDate":"2024-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139376212","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}
Chao Cheng , Hengyue Xu , Maomao Ni , Changfa Guo , Yuanyuan Zhao , Yong Hu
{"title":"Interfacial electron interactions governed photoactivity and selectivity evolution of carbon dioxide photoreduction with spinel cobalt oxide based hollow hetero-nanocubes","authors":"Chao Cheng , Hengyue Xu , Maomao Ni , Changfa Guo , Yuanyuan Zhao , Yong Hu","doi":"10.1016/j.apcatb.2024.123705","DOIUrl":"10.1016/j.apcatb.2024.123705","url":null,"abstract":"<div><p>In this work, an efficient CO<sub>2</sub> photoreduction catalyst based on Co<sub>3</sub>O<sub>4</sub>/ZnIn<sub>2</sub>S<sub>4</sub> hollow hetero-nanocubes is precisely constructed via an in-situ transformation of cobalt-organic framework followed by a solvothermal reaction. Comprehensive in-situ spectroscopic analyses and theoretical calculations have revealed that the critical interfacial electron interactions (IEIs) effects on both photoactivity evolution and selectivity modulation in the Co<sub>3</sub>O<sub>4</sub>/ZnIn<sub>2</sub>S<sub>4</sub> hetero-structure. As the content of ZnIn<sub>2</sub>S<sub>4</sub> increases in the hetero-structure, the photoactivity exhibits a volcano-like evolution profile but the CH<sub>4</sub> selectivity reduces monotonously. The improved photoactivity is attributed to the IEIs-promoted charge separation as well as the specific-surface-area effect in terms of electron unitization rate, and the electronic structure of Co<sub>3</sub>O<sub>4</sub> is tuned and the energy barrier for the key reaction intermediate *CHO is reduced, leading to improved CH<sub>4</sub> selection in comparison with bare Co<sub>3</sub>O<sub>4</sub>. The IEIs-mediated production selectivity is further verified by a Co<sub>3</sub>O<sub>4</sub>/CeO<sub>2</sub> heterojunction, indicating a certain universality of the IEI effect.</p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"345 ","pages":"Article 123705"},"PeriodicalIF":22.1,"publicationDate":"2024-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139376426","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}
Mengjiao Xie , Wentian Zheng , Meng Sun , Shijie You , Yanbiao Liu
{"title":"Sustainable water decontamination in a fluidic sequential electrochemical reactor","authors":"Mengjiao Xie , Wentian Zheng , Meng Sun , Shijie You , Yanbiao Liu","doi":"10.1016/j.apcatb.2024.123708","DOIUrl":"10.1016/j.apcatb.2024.123708","url":null,"abstract":"<div><p>Here, we demonstrate an integrated fluidic sequential electrochemical system for effective water decontamination. The system consists of a Ti mesh anode deposited with nanoscale IrO<sub>2</sub><span> and a CNT filter functionalized with nanoconfined Fe</span><sub>2</sub>O<sub>3</sub>. By conducting anodic oxygen evolution reaction (OER) and 2e<sup>–</sup> oxygen reduction reaction (ORR) sequential electrolysis, our system enables sustainable O<sub>2</sub> generation at the anode, followed by transformation of O<sub>2</sub> into H<sub>2</sub>O<sub>2</sub> at the cathode, which then led to the production of <sup>1</sup>O<sub>2</sub> in the presence of nanoconfined Fe<sub>2</sub>O<sub>3</sub>. No chemical inputs were needed nor side products occurred during the whole sequential electrochemical processes. The effectiveness of the system was evaluated using tetracycline as a model emerging contaminant. Recirculating at 3 mL min<sup>–1</sup>, the system exhibited negligible iron and iridium leaching (≤0.01 mg L<sup>–1</sup>) and high tetracycline degradation efficiency (≥95%). Such excellent efficacy can be maintained across a wide pH range and in complicated water matrices.</p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"345 ","pages":"Article 123708"},"PeriodicalIF":22.1,"publicationDate":"2024-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139376354","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}
Ximeng Xu , Shujing Zhang , Yuhao Wang , Nana Wang , Qinli Jiang , Xiaohong Liu , Qingqing Guan , Wei Zhang
{"title":"2D surfaces twisted to enhance electron freedom toward efficient advanced oxidation processes","authors":"Ximeng Xu , Shujing Zhang , Yuhao Wang , Nana Wang , Qinli Jiang , Xiaohong Liu , Qingqing Guan , Wei Zhang","doi":"10.1016/j.apcatb.2024.123701","DOIUrl":"10.1016/j.apcatb.2024.123701","url":null,"abstract":"<div><p>Two-dimensional (2D)-interface engineering for designing effective electron-rich catalyst center is pivotal in manipulating the catalytic behaviors and activity, but still challenging. Here, we’ve successfully twisted the surfaces of the 2D layered FeOCl, fulfilling the targeted fine-tuning of its Fe sites. The obtained new catalyst can boost peroxymonosulfate activation for reactive species with much lower energy barriers and efficiently oxidized target organic with almost 41 orders of magnitude faster reaction kinetics than pristine FeOCl. The increased degree of freedom of electron around Fe site has been identified as the key driver. The distorted geometry structure around Fe has led to an increased polarization of charge distribution, associating with less symmetric electron valence cloud and higher electron mobility. Thus, the twisted surfaces enable a much enhanced interfacial charge transfer between Fe site and the electron-deficient peroxymonosulfate. This work highlights the concept of twisted surface construction toward efficient advanced oxidation catalyst design.</p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"345 ","pages":"Article 123701"},"PeriodicalIF":22.1,"publicationDate":"2024-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139376389","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}
Lianglin Yan , Guojun Dong , Xiaojuan Huang , Yun Zhang , Yingpu Bi
{"title":"Unraveling oxygen vacancy changes of WO3 photoanodes for promoting oxygen evolution reaction","authors":"Lianglin Yan , Guojun Dong , Xiaojuan Huang , Yun Zhang , Yingpu Bi","doi":"10.1016/j.apcatb.2023.123682","DOIUrl":"10.1016/j.apcatb.2023.123682","url":null,"abstract":"<div><p>Oxygen vacancy (V<sub>O</sub><span>) on semiconductor photoanode plays an important role in enhancing photoelectrochemical water oxidation performances. Nonetheless, there is still a lack of definitive elucidation regarding the structural changes and their impact on charge transport during the oxygen evolution reaction (OER). Herein, oxygen vacancies were rationally introduced on WO</span><sub>3</sub> nanoflake photoanodes via Ar-plasma engraving, resulting in a threefold increase in the photocurrent density of 2.76 mA cm<sup>−2</sup> at 1.23 V<sub>RHE</sub> under AM 1.5 G solar irradiation compared to the pristine WO<sub>3</sub> photoanode. Comprehensive experiments and theoretical calculations reveal that the self-healing process of surface oxygen vacancies on WO<sub>3</sub> photoanodes should be more easily achieved by capturing oxygen atoms from adsorbed H<sub>2</sub>O molecules. However, some survived oxygen vacancies in the subsurface could effectively increase the charge carrier density and provide the additional driving force to accelerate the interfacial charge transport, leading to enhanced photoelectrochemical (PEC) activities. More importantly, the oxygen vacancy self-healing on metal-oxide semiconductors is a universal phenomenon, which might bring new insights for design and construction of highly efficient photoanodes for PEC water oxidation.</p></div>","PeriodicalId":244,"journal":{"name":"Applied Catalysis B: Environmental","volume":"345 ","pages":"Article 123682"},"PeriodicalIF":22.1,"publicationDate":"2024-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"139094462","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}