Pub Date : 2024-08-15DOI: 10.1016/j.apcatb.2024.124510
Yanyu Jin, Xing Yuan, Bin Zhou, Shengpeng Mo, Wenhua Zhang, Yue Peng, Qibao Wang, Junhua Li, Wenzhe Si
Transition-metal (TM) active centers are solely considered to probe the intrinsic origin of catalytic activity, but the interaction between metal and oxygen has been overlooked. Herein, an effective approach is demonstrated to adjust the degree of TM–O covalency, enhancing the intrinsic catalytic activity via Cu substitution and acid etching. spectroscopic investigations and theoretical calculations reveal that improved catalytic performances are attributed to enhanced TM–O covalency. Owing to the strong hybridization between TM 3d and O 2p orbitals, the intramolecular electrons are transported from oxygen to TM cations, promoting asymmetric electron redistribution and inducing oxygen holes (electrophilic O) generation. Ligand oxygen holes as preactive oxygen centers achieved the initial activation of reactant molecules and lattice oxygen activation, ultimately boosting the heterogeneous catalytic activity. The findings highlight a new method to design highly covalent perovskite oxides with sufficient ligand oxygen holes to trigger lattice oxygen activation in the catalytic fields.
过渡金属（TM）活性中心被认为是探究催化活性内在来源的唯一途径，但金属与氧之间的相互作用却被忽视了。光谱研究和理论计算表明，催化性能的提高归因于 TM-O 共价性的增强。由于 TM 3d 和 O 2p 轨道之间的强杂化作用，分子内电子从氧转移到 TM 阳离子，促进了电子的不对称再分布，诱导了氧洞（亲电性 O）的产生。配体氧洞作为前活性氧中心实现了反应物分子的初始活化和晶格氧活化，最终提高了异相催化活性。这些研究结果突显了一种新方法，可以设计出具有足够配体氧洞的高共价包晶氧化物，从而在催化领域引发晶格氧活化。
{"title":"Constructing active lattice oxygen in high covalent perovskites for boosting catalytic activity","authors":"Yanyu Jin, Xing Yuan, Bin Zhou, Shengpeng Mo, Wenhua Zhang, Yue Peng, Qibao Wang, Junhua Li, Wenzhe Si","doi":"10.1016/j.apcatb.2024.124510","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124510","url":null,"abstract":"Transition-metal (TM) active centers are solely considered to probe the intrinsic origin of catalytic activity, but the interaction between metal and oxygen has been overlooked. Herein, an effective approach is demonstrated to adjust the degree of TM–O covalency, enhancing the intrinsic catalytic activity via Cu substitution and acid etching. spectroscopic investigations and theoretical calculations reveal that improved catalytic performances are attributed to enhanced TM–O covalency. Owing to the strong hybridization between TM 3d and O 2p orbitals, the intramolecular electrons are transported from oxygen to TM cations, promoting asymmetric electron redistribution and inducing oxygen holes (electrophilic O) generation. Ligand oxygen holes as preactive oxygen centers achieved the initial activation of reactant molecules and lattice oxygen activation, ultimately boosting the heterogeneous catalytic activity. The findings highlight a new method to design highly covalent perovskite oxides with sufficient ligand oxygen holes to trigger lattice oxygen activation in the catalytic fields.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205163","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 : 2024-08-15DOI: 10.1016/j.apcatb.2024.124508
Mi Zhang, Kunpeng Li, Shicheng Yuan, Ruibin Lv, Hao Huang, Hui Hu, Jue Liu, Li Liu, Maohong Fan, Kaiyuan Li
Imidazolium-based ionic liquids (Imim-ILs) have great application potential in catalyzing the electrochemical CO reduction reaction (CORR). However, the microscopic mechanism by which imidazolium-based cations promote CORR remains unclear. In this study, we observe that despite the structural differences between [Bmmim] and [Bmim], both exhibit high catalytic activity during the electrochemical CORR. Electrochemical and in situ spectroscopic analyses, as well as Quantum Theory of Atomic in Molecules (QTAIM), reveal that the pivotal step in the CORR mechanism facilitated by [Bmmim] and [Bmim] involves the formation of [Bmmim]···CO or [Bmim]···CO complexes via hydrogen bond. These complexes enhance the electrochemical reduction of CO or ·CO on electrode, facilitating efficient CO production. Specifically, the [Bmmim]···CO complex forms at the C4-H position of the imidazole ring, while in the [Bmim]···CO complex, it forms at the C2-H position.
咪唑基离子液体（Imim-ILs）在催化电化学一氧化碳还原反应（CORR）方面具有巨大的应用潜力。然而，咪唑类阳离子促进 CORR 的微观机制仍不清楚。在本研究中，我们观察到尽管[Bmmim]和[Bmim]在结构上存在差异，但二者在电化学 CO 还原反应中都表现出很高的催化活性。电化学和原位光谱分析以及原子分子量子理论（QTAIM）揭示了[Bmmim]和[Bmim]促进 CORR 机制的关键步骤是通过氢键形成[Bmmim]--CO 或[Bmim]--CO 复合物。这些复合物可增强 CO 或 -CO 在电极上的电化学还原，从而促进 CO 的高效生产。具体来说，[Bmmim]---CO 复合物形成于咪唑环的 C4-H 位置，而[Bmim]---CO 复合物则形成于 C2-H 位置。
{"title":"Mechanism of efficient electroreduction of CO2 to CO at Ag electrode in imidazolium-based ionic liquids/acetonitrile solution","authors":"Mi Zhang, Kunpeng Li, Shicheng Yuan, Ruibin Lv, Hao Huang, Hui Hu, Jue Liu, Li Liu, Maohong Fan, Kaiyuan Li","doi":"10.1016/j.apcatb.2024.124508","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124508","url":null,"abstract":"Imidazolium-based ionic liquids (Imim-ILs) have great application potential in catalyzing the electrochemical CO reduction reaction (CORR). However, the microscopic mechanism by which imidazolium-based cations promote CORR remains unclear. In this study, we observe that despite the structural differences between [Bmmim] and [Bmim], both exhibit high catalytic activity during the electrochemical CORR. Electrochemical and in situ spectroscopic analyses, as well as Quantum Theory of Atomic in Molecules (QTAIM), reveal that the pivotal step in the CORR mechanism facilitated by [Bmmim] and [Bmim] involves the formation of [Bmmim]···CO or [Bmim]···CO complexes via hydrogen bond. These complexes enhance the electrochemical reduction of CO or ·CO on electrode, facilitating efficient CO production. Specifically, the [Bmmim]···CO complex forms at the C4-H position of the imidazole ring, while in the [Bmim]···CO complex, it forms at the C2-H position.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205174","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 : 2024-08-14DOI: 10.1016/j.apcatb.2024.124494
Atul Kumar, Rajat Ghalta, Rajaram Bal, Rajendra Srivastava
Converting lignin, a key sustainable biopolymer, into valuable oxygen-containing compounds is a significant challenge. To address such a challenge, photocatalytic self-transfer hydrogenolysis strategy is employed utilizing a CdS(x%)/TiO heterojunction photocatalyst, with minimal CdS loading on TiO. The CdS(3 %)/TiO catalyst, under blue light, dehydrogenates HC–OH groups, transferring hydrogen to C–O bonds, cleaving β-O-4 ether bonds in lignin model compounds yielding over 95 % phenols and acetophenones. It utilizes glyceryl moieties as a hydrogen source, yielding ∼ 24 % of diverse lignin monomer derivatives from teak lignin. Improved charge separation in the CdS(3 %)/TiO catalyst is revealed by electrochemical and spectral analyses and exhibits delayed charge carrier recombination. Scavenging studies confirm a type II charge transfer mechanism and support visible-light-driven lignin fragmentation. The present photocatalytic process offers a promising, cost-effective approach for converting lignin into valuable aromatic compounds, advancing renewable biomass-derived chemicals.
{"title":"Photocatalytic β-O-4 bond cleavage in lignin models and native lignin through CdS integration on titanium oxide photocatalyst under visible light irradiation","authors":"Atul Kumar, Rajat Ghalta, Rajaram Bal, Rajendra Srivastava","doi":"10.1016/j.apcatb.2024.124494","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124494","url":null,"abstract":"Converting lignin, a key sustainable biopolymer, into valuable oxygen-containing compounds is a significant challenge. To address such a challenge, photocatalytic self-transfer hydrogenolysis strategy is employed utilizing a CdS(x%)/TiO heterojunction photocatalyst, with minimal CdS loading on TiO. The CdS(3 %)/TiO catalyst, under blue light, dehydrogenates HC–OH groups, transferring hydrogen to C–O bonds, cleaving β-O-4 ether bonds in lignin model compounds yielding over 95 % phenols and acetophenones. It utilizes glyceryl moieties as a hydrogen source, yielding ∼ 24 % of diverse lignin monomer derivatives from teak lignin. Improved charge separation in the CdS(3 %)/TiO catalyst is revealed by electrochemical and spectral analyses and exhibits delayed charge carrier recombination. Scavenging studies confirm a type II charge transfer mechanism and support visible-light-driven lignin fragmentation. The present photocatalytic process offers a promising, cost-effective approach for converting lignin into valuable aromatic compounds, advancing renewable biomass-derived chemicals.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205168","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 : 2024-08-14DOI: 10.1016/j.apcatb.2024.124503
Li Xu, Meihua Li, Fangming Zhao, Jingjing Quan, Xingming Ning, Pei Chen, Zhongwei An, Xinbing Chen
The loading of transition metal oxyhydroxide (TMOH) on semiconductor (SC) is a promising strategy for fabricating desired photoelectrochemical (PEC) devices. Nevertheless, the inevitable charge recombination occurring at SC/TMOH interface severely hinders the carrier transfer. Herein, differing from the conventional multi-step hole capture process, a novel transition metal-based interfacial regulation layer with low oxidation state species is introduced for boosted charge separation. As expected, the optimized BiVO/Cu-CoO/FeNiOOH photoanode obtains a photocurrent density of 6.60 mA/cm at 1.23 V versus reversible hydrogen electrode (RHE) accompanied with outstanding photostability. ultraviolet/visible-spectroelectrochemistry, electrochemical analyses, and density functional theory (DFT) show that the Cu-CoO, like “charge transporter”, can directly modulate charge transfer pathway and quickly transfer hole from BiVO to FeNiOOH surface for PEC water splitting. Moreover, the approach can be extended to other Cu-NiO and Mn-CoO, proving its universality. This work provides an effective strategy to design efficient and stable photoanodes for water splitting.
{"title":"Low oxidation state engineering in transition metal-based interfacial regulation layer accelerates charge transfer kinetics toward enhanced photoelectrochemical water splitting","authors":"Li Xu, Meihua Li, Fangming Zhao, Jingjing Quan, Xingming Ning, Pei Chen, Zhongwei An, Xinbing Chen","doi":"10.1016/j.apcatb.2024.124503","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124503","url":null,"abstract":"The loading of transition metal oxyhydroxide (TMOH) on semiconductor (SC) is a promising strategy for fabricating desired photoelectrochemical (PEC) devices. Nevertheless, the inevitable charge recombination occurring at SC/TMOH interface severely hinders the carrier transfer. Herein, differing from the conventional multi-step hole capture process, a novel transition metal-based interfacial regulation layer with low oxidation state species is introduced for boosted charge separation. As expected, the optimized BiVO/Cu-CoO/FeNiOOH photoanode obtains a photocurrent density of 6.60 mA/cm at 1.23 V versus reversible hydrogen electrode (RHE) accompanied with outstanding photostability. ultraviolet/visible-spectroelectrochemistry, electrochemical analyses, and density functional theory (DFT) show that the Cu-CoO, like “charge transporter”, can directly modulate charge transfer pathway and quickly transfer hole from BiVO to FeNiOOH surface for PEC water splitting. Moreover, the approach can be extended to other Cu-NiO and Mn-CoO, proving its universality. This work provides an effective strategy to design efficient and stable photoanodes for water splitting.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226227","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 : 2024-08-14DOI: 10.1016/j.apcatb.2024.124491
Huayong Yang, Guowei Liu, Lixiao Zheng, Min Zhang, Zhongjie Guan, Taifeng Liu, Jianjun Yang
Improving the CO to CH conversion efficiency of Cu metal-organic frameworks (Cu-MOFs) catalysts is important for promoting carbon capture and utilization. In this work, a series of novel Cu-Fe bimetallic MOFs photocatalysts (Cu-BTB-Fe with 0.5 wt%, 1.0 wt%, 2.0 wt%, and 4.0 wt% of Fe; HBTB = 1,3,5-tris(4-carboxyphenyl) benzene) were synthesized by a bimetallic site (Cu and Fe) design strategy in order to improve the electron-hole separation efficiency and CO adsorption activation. Findings indicated that the as-synthesized Cu-BTB-2 wt% Fe catalyst exhibited excellent catalytic performance for the conversion of CO to CH and CO under simulated sunlight irradiation, providing a yield of 32.20 mol∙g∙h and a selectivity of 69.24 % for CO to CH conversion as well as a yield of 14.29 mol∙g∙h for CO to CO conversion without liquid phase products. This is because the Cu-Fe bimetallic sites can continuously supply photoinduced electrons with long separated-state decay lifetime to efficiently activate CO. Specifically, the Cu-BTB-Fe catalysts provided a high proportion of effective photoinduced electrons with long decay lifetime for the CO* hydrogenation process through a unique electron transfer mechanism, while the strong affinity between CO and [Cu(COO)]-Fe active units enabled high CO adsorption activation and rapid CO reduction. The present approach, hopefully, would help to establish feasible pathway for the development of novel highly selective Cu-based MOFs photocatalysts for CO photocatalytic reduction yielding CH.
提高铜金属有机框架（Cu-MOFs）催化剂的 CO 到 CH 转化效率对于促进碳捕集与利用非常重要。本研究采用双金属位点（Cu 和 Fe）设计策略合成了一系列新型 Cu-Fe 双金属 MOFs 光催化剂（Cu-BTB-Fe，Fe 的含量分别为 0.5 wt%、1.0 wt%、2.0 wt% 和 4.0 wt%；HBTB = 1,3,5-三（4-羧基苯基）苯），以提高电子-空穴分离效率和 CO 吸附活化能力。研究结果表明，在模拟阳光照射下，合成的 Cu-BTB-2 wt% Fe 催化剂在将 CO 转化为 CH 和 CO 方面表现出优异的催化性能，将 CO 转化为 CH 的产率为 32.20 mol∙g∙h，选择性为 69.24 %；将 CO 转化为 CO 的产率为 14.29 mol∙g∙h，且无液相产物。这是因为 Cu-Fe 双金属位点可以持续提供分离态衰变寿命长的光诱导电子，从而有效地活化 CO。具体来说，Cu-BTB-Fe 催化剂通过独特的电子传递机制为 CO* 加氢过程提供了高比例、长衰变寿命的有效光诱导电子，而 CO 与[Cu(COO)]-Fe 活性单元之间的强亲和力使 CO 吸附活化率高，并能快速还原 CO。希望本研究方法能为开发新型高选择性 Cu 基 MOFs 光催化剂提供可行的途径，用于 CO 光催化还原生成 CH。
{"title":"Cu-Fe bimetallic MOFs with long lifetime separated-state charge for enhancing selectivity for CO2 photoreduction to CH4","authors":"Huayong Yang, Guowei Liu, Lixiao Zheng, Min Zhang, Zhongjie Guan, Taifeng Liu, Jianjun Yang","doi":"10.1016/j.apcatb.2024.124491","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124491","url":null,"abstract":"Improving the CO to CH conversion efficiency of Cu metal-organic frameworks (Cu-MOFs) catalysts is important for promoting carbon capture and utilization. In this work, a series of novel Cu-Fe bimetallic MOFs photocatalysts (Cu-BTB-Fe with 0.5 wt%, 1.0 wt%, 2.0 wt%, and 4.0 wt% of Fe; HBTB = 1,3,5-tris(4-carboxyphenyl) benzene) were synthesized by a bimetallic site (Cu and Fe) design strategy in order to improve the electron-hole separation efficiency and CO adsorption activation. Findings indicated that the as-synthesized Cu-BTB-2 wt% Fe catalyst exhibited excellent catalytic performance for the conversion of CO to CH and CO under simulated sunlight irradiation, providing a yield of 32.20 mol∙g∙h and a selectivity of 69.24 % for CO to CH conversion as well as a yield of 14.29 mol∙g∙h for CO to CO conversion without liquid phase products. This is because the Cu-Fe bimetallic sites can continuously supply photoinduced electrons with long separated-state decay lifetime to efficiently activate CO. Specifically, the Cu-BTB-Fe catalysts provided a high proportion of effective photoinduced electrons with long decay lifetime for the CO* hydrogenation process through a unique electron transfer mechanism, while the strong affinity between CO and [Cu(COO)]-Fe active units enabled high CO adsorption activation and rapid CO reduction. The present approach, hopefully, would help to establish feasible pathway for the development of novel highly selective Cu-based MOFs photocatalysts for CO photocatalytic reduction yielding CH.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226228","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 : 2024-08-14DOI: 10.1016/j.apcatb.2024.124507
Xiaokang Chu, Yuxiao Lin, Hang Chen, Qingxue Lai, Luanjie Nie, Hao Wang, Ran Chen, Rongxin Ma, Yunsong Li, Zixia Lin, Jing Zheng
Electrolyte engineering strategy has attracted high expectations for addressing the universally existed serious dynamics and thermodynamics issues in potassium-ion batteries (PIBs), especially for the batteries adopted with organic electrode materials. Herein, a new kind of ester-ether hybrid electrolytes (EEHEs) was developed with widely manipulatable solvation structures from solvent-separated ion pair (SSIP) to aggregate (AGG)-dominated states for PIBs. The optimized EEHEs of 5 M KFSI/EC+DME enabled high Coulombic efficiency and ultra-stable K plating/stripping stability in K||Cu cells and K||K symmetric cells, respectively. When the developed novel organic anode material of 2-Bromobenzene-1,3-dialdehyde/carbon nanotube (BBD/CNT) was matched with the 5 M KFSI/EC+DME electrolyte, it delivered a reversible capacity of about 288 mAh g at 50 mA g and approximately 244 mAh g at 200 mA g with negligible capacity fade. The excellent performance should be attributed to the surface capacitive-dominated mechanism with fast K-storage kinetics guaranteed by the AGG-dominated solvation structures.
电解质工程策略在解决钾离子电池（PIBs）中普遍存在的严重动力学和热力学问题方面被寄予厚望，尤其是对于采用有机电极材料的电池。在此，我们开发了一种新型酯醚混合电解质（EEHEs），其溶解结构从溶剂分离离子对（SSIP）到聚合体（AGG）为主的状态均可广泛操作，适用于 PIBs。优化后的 5 M KFSI/EC+DME EEHEs 可分别在 K||Cu 电池和 K||K 对称电池中实现高库仑效率和超稳定的 K plating/stripping 稳定性。当所开发的新型 2-溴苯-1,3-二甲醛/碳纳米管（BBD/CNT）有机负极材料与 5 M KFSI/EC+DME 电解液相匹配时，在 50 mA g 和 200 mA g 条件下分别可产生约 288 mAh g 和约 244 mAh g 的可逆容量，且容量衰减几乎可以忽略不计。优异的性能应归功于以 AGG 为主导的溶解结构所保证的表面电容主导机制和快速 K 储存动力学。
{"title":"Designing ester-ether hybrid electrolytes for aldehyde-based organic anode to achieve superior K-storage","authors":"Xiaokang Chu, Yuxiao Lin, Hang Chen, Qingxue Lai, Luanjie Nie, Hao Wang, Ran Chen, Rongxin Ma, Yunsong Li, Zixia Lin, Jing Zheng","doi":"10.1016/j.apcatb.2024.124507","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124507","url":null,"abstract":"Electrolyte engineering strategy has attracted high expectations for addressing the universally existed serious dynamics and thermodynamics issues in potassium-ion batteries (PIBs), especially for the batteries adopted with organic electrode materials. Herein, a new kind of ester-ether hybrid electrolytes (EEHEs) was developed with widely manipulatable solvation structures from solvent-separated ion pair (SSIP) to aggregate (AGG)-dominated states for PIBs. The optimized EEHEs of 5 M KFSI/EC+DME enabled high Coulombic efficiency and ultra-stable K plating/stripping stability in K||Cu cells and K||K symmetric cells, respectively. When the developed novel organic anode material of 2-Bromobenzene-1,3-dialdehyde/carbon nanotube (BBD/CNT) was matched with the 5 M KFSI/EC+DME electrolyte, it delivered a reversible capacity of about 288 mAh g at 50 mA g and approximately 244 mAh g at 200 mA g with negligible capacity fade. The excellent performance should be attributed to the surface capacitive-dominated mechanism with fast K-storage kinetics guaranteed by the AGG-dominated solvation structures.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226240","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}
Achieving a high yield of oxygenates and inhibiting overoxidation remain challenging for CH photooxidation. Here, we report a catalyst with enriched Ag-ZnO interfaces by using ZIF-8 as the precursor. The resulting Ag/Z-450 photocatalysts show extraordinary efficiency in the photocatalytic oxidation of CH, a high liquid oxygenate yield of 57.88 mmol·g (28.94 mmol·g·h) and a selectivity of ∼100 % were obtained over 3.0Ag/Z-450, with HCHO as the major product (41.04 mmol·g, ∼71 % selectivity). Mechanistic studies revealed that ZnO and Ag species acted as electron donors and acceptors, respectively, which enhanced charge carriers transfer and separation. CH and O can be effectively activated to generate •CH and reactive oxygen species (ROS), their following reaction led to formation of CHOOH, which can be further converted to CHOH and HCHO. This work contributes to the development of a “two-in-one” CH photooxidation catalyst system that simultaneously achieves unparallel productivity and selectivity.
{"title":"ZIF-8 derived Ag/ZnO photocatalyst with enriched Ag-ZnO interface for effective oxidation of methane to liquid oxygenates with simultaneous mmol-scale productivity and ∼100 % selectivity","authors":"Yingdong Hao, Yonghui Zhao, Chunlai Zhang, Xinqing Chen, Nannan Sun, Wei Wei","doi":"10.1016/j.apcatb.2024.124505","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124505","url":null,"abstract":"Achieving a high yield of oxygenates and inhibiting overoxidation remain challenging for CH photooxidation. Here, we report a catalyst with enriched Ag-ZnO interfaces by using ZIF-8 as the precursor. The resulting Ag/Z-450 photocatalysts show extraordinary efficiency in the photocatalytic oxidation of CH, a high liquid oxygenate yield of 57.88 mmol·g (28.94 mmol·g·h) and a selectivity of ∼100 % were obtained over 3.0Ag/Z-450, with HCHO as the major product (41.04 mmol·g, ∼71 % selectivity). Mechanistic studies revealed that ZnO and Ag species acted as electron donors and acceptors, respectively, which enhanced charge carriers transfer and separation. CH and O can be effectively activated to generate •CH and reactive oxygen species (ROS), their following reaction led to formation of CHOOH, which can be further converted to CHOH and HCHO. This work contributes to the development of a “two-in-one” CH photooxidation catalyst system that simultaneously achieves unparallel productivity and selectivity.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205175","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 : 2024-08-13DOI: 10.1016/j.apcatb.2024.124500
Yiqi Zhang, Denghui Ma, Shujuan Jiang, Jianjun Zhang, Shaoqing Song
The lowered reaction energy barrier and accelerated dynamic behavior for photocatalytic HO overall splitting (HOS) involving oriented chemisorption, activation and conversion of *H and oxyhydrogen intermediates are crucial for solar energy conversion into H (STH). Herein, the localized heterojunction (Cd-S-Ni) composed of NiS and CdS tuning surface atomic arrangement with S atoms as the shared ligands has been constructed to synchronously elevate and optimize Ni 3 (Ni ) and S 2 (S ) band centers as efficient active sites for chemisorption of oxyhydrogen and *H intermediates with a declined Cd 4 band center (Cd ) to suppress reverse reaction. A sustainable STH of 3.21 % under AM 1.5 G has been completed over Cd-S-Ni with a decreased activation energy for H evolution, verified by fs-TAS, DRIFTS and dynamic DFT. These results devote to solving the reaction energy barrier and dynamical bottleneck for HOS by optimizing and .
降低光催化HO整体分裂（HOS）的反应能垒和加速其动态行为，包括*H和氢氧中间产物的定向化学吸附、活化和转化，对于太阳能转化为H（STH）至关重要。在此，我们构建了由 NiS 和 CdS 调整表面原子排列组成的局部异质结 (Cd-S-Ni)，以 S 原子作为共享配体，同步提升和优化 Ni 3 (Ni ) 和 S 2 (S ) 带中心，使其成为氧氢和 *H 中间体化学吸附的高效活性位点，同时降低 Cd 4 带中心 (Cd ) 以抑制反向反应。通过fs-TAS、DRIFTS 和动态 DFT 验证，在 AM 1.5 G 条件下，Cd-S-Ni 的 STH 可持续达到 3.21%，H 演化的活化能也有所降低。这些结果有助于通过优化和...
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The poor stability of nanoparticle catalysts with catalytic activity is a significant obstacle to their industrial application. The establishment of rational nanoparticle structures to elucidate the relationship between catalyst structure and its catalytic activity and stability is crucial for constructing nanoparticle catalysts that are both highly active and stable. We propose a strategy to construct a dual-confinement effect of the nanoparticle, specifically by regulating the polarization of the MnNiO support to enhance strong oxide-support interactions (SOSI) and encapsulating the outer layer of nanoparticles with a carbon shell, which has been proven effective in improving the activity and stability of nanoparticle-based oxygen evolution reaction (OER) electrocatalysts. At a current density of 100 mA cm, the armor C@RuO@MnNiO catalyst displays an overpotential of 260 mV for the OER. After the OER test for 100 h, the current density of C@RuO@MnNiO shows no significant decay, whereas that of RuO@MnNiO and RuO@MnO rapidly decreases, indicating significant catalytic activity and stability of the catalyst. The assembled C@RuO@MnNiO||Pt/C electrode demonstrates excellent alkaline water electrolysis performance in an MEA electrolyzer, requiring only a low cell voltage of 1.76 V to achieve an ampere-level current density of 1 A cm. In-situ electrochemical Raman spectroscopy reveals the significant interaction between nanoparticles and the polar support. The reduction in Gibbs free energy, which establishes the rate-determining step (RDS) of OER, is caused by the charge redistribution caused by polar Mn doping in RuO@MnNiO and the coordination structure modifications, as shown by density functional theory calculations. This work provides an approach to designing efficient and stable nanoparticle electrocatalysts through the dual-confinement effect of SOSI-induced strong interactions and armor carbon layers.
具有催化活性的纳米粒子催化剂稳定性差，是其工业应用的一大障碍。建立合理的纳米粒子结构，阐明催化剂结构与其催化活性和稳定性之间的关系，对于构建高活性和高稳定性的纳米粒子催化剂至关重要。我们提出了一种构建纳米粒子双重约束效应的策略，特别是通过调节 MnNiO 支承的极化来增强强氧化物-支承相互作用（SOSI），并用碳壳包裹纳米粒子外层，这已被证明能有效提高基于纳米粒子的氧进化反应（OER）电催化剂的活性和稳定性。在 100 mA cm 的电流密度下，铠装 C@RuO@MnNiO 催化剂的 OER 过电位为 260 mV。经过 100 h 的 OER 测试后，C@RuO@MnNiO 的电流密度没有明显衰减，而 RuO@MnNiO 和 RuO@MnO 的电流密度则迅速下降，这表明催化剂具有显著的催化活性和稳定性。组装好的 C@RuO@MnNiO||Pt/C 电极在 MEA 电解槽中表现出优异的碱性水电解性能，只需要 1.76 V 的低电池电压就能达到 1 A cm 的安培级电流密度。原位电化学拉曼光谱揭示了纳米颗粒与极性支持物之间的显著相互作用。密度泛函理论计算表明，吉布斯自由能的降低是由 RuO@MnNiO 中极性锰掺杂引起的电荷再分布和配位结构的改变造成的，而吉布斯自由能的降低确立了 OER 的速率决定步骤 (RDS)。这项工作为通过 SOSI 诱导的强相互作用和铠装碳层的双重约束效应设计高效稳定的纳米粒子电催化剂提供了一种方法。
{"title":"Dual confinement of RuOx nanoparticle using polar MnNiO and armored carbon for boosting water electrolysis","authors":"Ning Wen, Xiaoxiao Duan, Ruiying Chai, Xiuling Jiao, Yuguo Xia, Dairong Chen","doi":"10.1016/j.apcatb.2024.124504","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124504","url":null,"abstract":"The poor stability of nanoparticle catalysts with catalytic activity is a significant obstacle to their industrial application. The establishment of rational nanoparticle structures to elucidate the relationship between catalyst structure and its catalytic activity and stability is crucial for constructing nanoparticle catalysts that are both highly active and stable. We propose a strategy to construct a dual-confinement effect of the nanoparticle, specifically by regulating the polarization of the MnNiO support to enhance strong oxide-support interactions (SOSI) and encapsulating the outer layer of nanoparticles with a carbon shell, which has been proven effective in improving the activity and stability of nanoparticle-based oxygen evolution reaction (OER) electrocatalysts. At a current density of 100 mA cm, the armor C@RuO@MnNiO catalyst displays an overpotential of 260 mV for the OER. After the OER test for 100 h, the current density of C@RuO@MnNiO shows no significant decay, whereas that of RuO@MnNiO and RuO@MnO rapidly decreases, indicating significant catalytic activity and stability of the catalyst. The assembled C@RuO@MnNiO||Pt/C electrode demonstrates excellent alkaline water electrolysis performance in an MEA electrolyzer, requiring only a low cell voltage of 1.76 V to achieve an ampere-level current density of 1 A cm. In-situ electrochemical Raman spectroscopy reveals the significant interaction between nanoparticles and the polar support. The reduction in Gibbs free energy, which establishes the rate-determining step (RDS) of OER, is caused by the charge redistribution caused by polar Mn doping in RuO@MnNiO and the coordination structure modifications, as shown by density functional theory calculations. This work provides an approach to designing efficient and stable nanoparticle electrocatalysts through the dual-confinement effect of SOSI-induced strong interactions and armor carbon layers.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226241","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 : 2024-08-13DOI: 10.1016/j.apcatb.2024.124506
Xian Wang, Ze Qin, Jinjie Qian, Liyu Chen, Kui Shen
Developing low-cost but efficient electrocatalysts for continuous oxygen evolution reaction (OER) at ampere-level current densities can promote the hydrogen economy. LDHs are promising electrocatalysts to replace noble-metal-based catalysts for efficient OER, and rationally constructing LDH-based heterostructures can further boost their OER activities. Herein, we report the anchoring of FeNi-LDH nanoflakes onto MOF-derived carbon nanotube (CNT) networks on carbon cloth to obtain the self-supported LDH/CNT/CC. Benefiting from the advantages of its CNT network and the highly-active sites of its three-layer heterostructure, the optimized LDH/CNT/CC only requires a low overpotential of 200 mV at 10 mA cm and exhibits robust stability under continuous electrolysis for 160 h at an ampere-level current density of 1 A cm. Theoretical calculations show three-layer FeNi-LDH(001)/graphene(002)/Co(111) slab has the lowest OER energy barrier, and its graphene layer can gain electrons from the FeNi-LDH and Co to show the most suitable binding strength for intermediates to facilitate OER.
开发低成本但高效的电催化剂，用于安培级电流密度的连续氧进化反应（OER），可以促进氢经济的发展。基于 LDH 的异质结构可进一步提高其 OER 活性。在此，我们报告了将 FeNi-LDH 纳米片锚定到碳布上的 MOF 衍生碳纳米管（CNT）网络上，从而获得自支撑 LDH/CNT/CC。得益于碳纳米管网络的优势和三层异质结构的高活性位点，优化后的 LDH/CNT/CC 在 10 mA cm 的条件下只需 200 mV 的低过电位，并在 1 A cm 的安培级电流密度下连续电解 160 小时，表现出极强的稳定性。理论计算表明，三层 FeNi-LDH(001)/graphene(002)/Co(111) 板具有最低的 OER 能量势垒，其石墨烯层可以从 FeNi-LDH 和 Co 中获得电子，从而显示出最合适的中间体结合强度，促进 OER。
{"title":"FeNi-LDH nanoflakes on Co-encapsulated CNT networks for stable and efficient ampere-level current density oxygen evolution","authors":"Xian Wang, Ze Qin, Jinjie Qian, Liyu Chen, Kui Shen","doi":"10.1016/j.apcatb.2024.124506","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124506","url":null,"abstract":"Developing low-cost but efficient electrocatalysts for continuous oxygen evolution reaction (OER) at ampere-level current densities can promote the hydrogen economy. LDHs are promising electrocatalysts to replace noble-metal-based catalysts for efficient OER, and rationally constructing LDH-based heterostructures can further boost their OER activities. Herein, we report the anchoring of FeNi-LDH nanoflakes onto MOF-derived carbon nanotube (CNT) networks on carbon cloth to obtain the self-supported LDH/CNT/CC. Benefiting from the advantages of its CNT network and the highly-active sites of its three-layer heterostructure, the optimized LDH/CNT/CC only requires a low overpotential of 200 mV at 10 mA cm and exhibits robust stability under continuous electrolysis for 160 h at an ampere-level current density of 1 A cm. Theoretical calculations show three-layer FeNi-LDH(001)/graphene(002)/Co(111) slab has the lowest OER energy barrier, and its graphene layer can gain electrons from the FeNi-LDH and Co to show the most suitable binding strength for intermediates to facilitate OER.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226243","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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