Yanyu Jin, Xing Yuan, Bin Zhou, Shengpeng Mo, Wenhua Zhang, Yue Peng, Qibao Wang, Junhua Li, Wenzhe Si
{"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":"23 1","pages":""},"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}
Mi Zhang, Kunpeng Li, Shicheng Yuan, Ruibin Lv, Hao Huang, Hui Hu, Jue Liu, Li Liu, Maohong Fan, Kaiyuan Li
{"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":"25 1","pages":""},"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}
Atul Kumar, Rajat Ghalta, Rajaram Bal, Rajendra Srivastava
{"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":"23 1","pages":""},"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}
Li Xu, Meihua Li, Fangming Zhao, Jingjing Quan, Xingming Ning, Pei Chen, Zhongwei An, Xinbing Chen
{"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":"4 1","pages":""},"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}
Huayong Yang, Guowei Liu, Lixiao Zheng, Min Zhang, Zhongjie Guan, Taifeng Liu, Jianjun Yang
{"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":"44 1","pages":""},"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}
Xiaokang Chu, Yuxiao Lin, Hang Chen, Qingxue Lai, Luanjie Nie, Hao Wang, Ran Chen, Rongxin Ma, Yunsong Li, Zixia Lin, Jing Zheng
{"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":"11 1","pages":""},"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}
{"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":"23 1","pages":""},"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}
Yiqi Zhang, Denghui Ma, Shujuan Jiang, Jianjun Zhang, Shaoqing Song
{"title":"Optimization of d-p band centers as efficient active sites for solar energy conversion into H2 by tuning surface atomic arrangement","authors":"Yiqi Zhang, Denghui Ma, Shujuan Jiang, Jianjun Zhang, Shaoqing Song","doi":"10.1016/j.apcatb.2024.124500","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124500","url":null,"abstract":"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 .","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":"59 1","pages":""},"PeriodicalIF":0.0,"publicationDate":"2024-08-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205169","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}
{"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":"61 1","pages":""},"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}
Xian Wang, Ze Qin, Jinjie Qian, Liyu Chen, Kui Shen
{"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":"1 1","pages":""},"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}