The complex active site configurations of high entropy alloys (HEAs) limit their performance optimization and wide applications. Herein, we report a FeCoNiMnRuLa/CNT catalyst for efficient electrocatalytic water splitting by introducing La to break the lattice ordering of FeCoNiMnRu. The introduction of La reduces the number of unpaired electrons in FeCoNiMnRu, which in turn accelerates the transition of singlet state oxygen-containing intermediate to triplet state oxygen. The DFT results verify that the lattice distortion exacerbated by La alters the d-orbital electronic configuration of FeCoNiMnRu, so that Fe and Ni play an important role in the critical adsorption of *OH in the OER as well as *HO in the HER, and Ru, Co, and Mn provide a strong safeguard for the desorption of oxygen-containing intermediates, thereby retaining excellent activity and stability during water decomposition. Our work showcases that the incorporation of rare earth elements opens new opportunities to improve the performance of HEAs.
高熵合金 (HEA) 复杂的活性位点构型限制了其性能优化和广泛应用。在此，我们报告了一种用于高效电催化水分离的 FeCoNiMnRuLa/CNT 催化剂，该催化剂通过引入 La 来打破 FeCoNiMnRu 的晶格有序性。La 的引入减少了 FeCoNiMnRu 中未配对电子的数量，进而加速了单线态含氧中间体向三线态氧的转变。DFT 结果验证了 La 加剧的晶格畸变改变了 FeCoNiMnRu 的 d-轨道电子构型，从而使 Fe 和 Ni 在 OER 中对 *OH 以及 HER 中对 *HO 的临界吸附中发挥了重要作用，而 Ru、Co 和 Mn 则为含氧中间体的解吸提供了强有力的保障，从而在水分解过程中保持了优异的活性和稳定性。我们的工作表明，稀土元素的加入为提高 HEA 的性能带来了新的机遇。
{"title":"La-exacerbated lattice distortion of high entropy alloys for enhanced electrocatalytic water splitting","authors":"Zhen-Long Wang, Gao-Yuan Huang, Guan-Rong Zhu, Huan-Chuan Hu, Cong Li, Xue-Han Guan, Hai-Bin Zhu","doi":"10.1016/j.apcatb.2024.124585","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124585","url":null,"abstract":"The complex active site configurations of high entropy alloys (HEAs) limit their performance optimization and wide applications. Herein, we report a FeCoNiMnRuLa/CNT catalyst for efficient electrocatalytic water splitting by introducing La to break the lattice ordering of FeCoNiMnRu. The introduction of La reduces the number of unpaired electrons in FeCoNiMnRu, which in turn accelerates the transition of singlet state oxygen-containing intermediate to triplet state oxygen. The DFT results verify that the lattice distortion exacerbated by La alters the d-orbital electronic configuration of FeCoNiMnRu, so that Fe and Ni play an important role in the critical adsorption of *OH in the OER as well as *HO in the HER, and Ru, Co, and Mn provide a strong safeguard for the desorption of oxygen-containing intermediates, thereby retaining excellent activity and stability during water decomposition. Our work showcases that the incorporation of rare earth elements opens new opportunities to improve the performance of HEAs.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250059","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 : 2024-09-08DOI: 10.1016/j.apcatb.2024.124580
Yunzhe Zheng, Xinhao Wang, Yudan Dong, Xiaoyu Wu, Donghua Xie, Yang Liu, Peng Zhou, Zhaokun Xiong, Chuan-Shu He, Bo Lai
This work comprehensively investigated how the characteristics of boron (B) precursors affect the catalytic activity of microscale zero-valent iron (mZVI) towards peracetic acid (PAA) activation for micropollutant degradation. Three boron precursors were introduced into mZVI by ball milling with their physical-chemical properties carefully characterized, and their ability to activate PAA comprehensively evaluated via sulfamethoxazole (SMX) oxidation efficiency. It’s found that BO-ZVI demonstrated the highest capability to activate PAA for SMX degradation, with 2 ∼ 3 times higher than NaBO-ZVI and HBO-ZVI. Specially, B precursors regulate the ability of mZVI to activate PAA via the following two aspects: (1) affecting the formation and content of FeB to accelerate Fe(II) regeneration; (2) increasing the hydrophilicity of the iron particles and the affinity of B-ZVI for binding PAA to different extent. This study highlights the important role of boron precursors in tuning engineered mZVI to initiate Fenton-like process for water purification.
{"title":"Overlooked role of boron precursors in tuning engineered zero-valent iron to activate peracetic acid for sustainable micropollutant oxidation","authors":"Yunzhe Zheng, Xinhao Wang, Yudan Dong, Xiaoyu Wu, Donghua Xie, Yang Liu, Peng Zhou, Zhaokun Xiong, Chuan-Shu He, Bo Lai","doi":"10.1016/j.apcatb.2024.124580","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124580","url":null,"abstract":"This work comprehensively investigated how the characteristics of boron (B) precursors affect the catalytic activity of microscale zero-valent iron (mZVI) towards peracetic acid (PAA) activation for micropollutant degradation. Three boron precursors were introduced into mZVI by ball milling with their physical-chemical properties carefully characterized, and their ability to activate PAA comprehensively evaluated via sulfamethoxazole (SMX) oxidation efficiency. It’s found that BO-ZVI demonstrated the highest capability to activate PAA for SMX degradation, with 2 ∼ 3 times higher than NaBO-ZVI and HBO-ZVI. Specially, B precursors regulate the ability of mZVI to activate PAA via the following two aspects: (1) affecting the formation and content of FeB to accelerate Fe(II) regeneration; (2) increasing the hydrophilicity of the iron particles and the affinity of B-ZVI for binding PAA to different extent. This study highlights the important role of boron precursors in tuning engineered mZVI to initiate Fenton-like process for water purification.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249997","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}
Covalent organic frameworks (COFs) have gained significant attention in environmental remediation. In this paper, we synthesized two sp carbon-conjugated COFs (HDU-107 and HDU-108) using [1,1′:4′,1''-terphenyl]-4,4''-dicarbonitrile and 2,2′-(benzo[][1,2,5]thiadiazole-4,7-diylbis(4,1-phenylene))diacetonitrile as the core, and benzo[1,2-b:3,4-b′:5,6-b″]trithiophene-2,5,8-tricarbaldehyde as the linker, for efficient photocatalytic reduction of Chromium (VI) (Cr(VI)). HDU-108 successfully constructed an electron donor-acceptor (D-A) structure using electron-rich thiophene as the electron donor and benzothiadiazole as the acceptor, exhibiting excellent photocatalytic ability due to its structure, which facilitated the spatial separation of charge carriers and reduced charge complexation. This ability was far superior to that of HDU-107. For 10 mg of HDU-108, the efficiency of Cr(VI) reduction in 120 minutes was more than 99.9 %. And the cycle experiments confirmed its good reusability and stability. e played a dominant role in the photoreduction of Cr(VI). Moreover, density-functional theory (DFT) simulations indicated that constructing D-A structures was an effective strategy for modulating photocatalytic activity. The charge separation was triggered by the polarization of the electron-rich BTT nucleus to the local charge density, while the cyanine conjugation provided the active center to concentrate the electronegativity. In conclusion, HDU-108, is expected to be a highly efficient photocatalytic material for environmental remediation.
{"title":"Highly crystalline benzothiadiazole covalent organic framework for enhanced Cr(VI) photocatalytic reduction by constructing donor-acceptor structure","authors":"Chen Wang, Wen Lu, Wenhui Song, Zhixiong Zhang, Chengde Xie, Yu Li, Jianjun Wang","doi":"10.1016/j.apcatb.2024.124583","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124583","url":null,"abstract":"Covalent organic frameworks (COFs) have gained significant attention in environmental remediation. In this paper, we synthesized two sp carbon-conjugated COFs (HDU-107 and HDU-108) using [1,1′:4′,1''-terphenyl]-4,4''-dicarbonitrile and 2,2′-(benzo[][1,2,5]thiadiazole-4,7-diylbis(4,1-phenylene))diacetonitrile as the core, and benzo[1,2-b:3,4-b′:5,6-b″]trithiophene-2,5,8-tricarbaldehyde as the linker, for efficient photocatalytic reduction of Chromium (VI) (Cr(VI)). HDU-108 successfully constructed an electron donor-acceptor (D-A) structure using electron-rich thiophene as the electron donor and benzothiadiazole as the acceptor, exhibiting excellent photocatalytic ability due to its structure, which facilitated the spatial separation of charge carriers and reduced charge complexation. This ability was far superior to that of HDU-107. For 10 mg of HDU-108, the efficiency of Cr(VI) reduction in 120 minutes was more than 99.9 %. And the cycle experiments confirmed its good reusability and stability. e played a dominant role in the photoreduction of Cr(VI). Moreover, density-functional theory (DFT) simulations indicated that constructing D-A structures was an effective strategy for modulating photocatalytic activity. The charge separation was triggered by the polarization of the electron-rich BTT nucleus to the local charge density, while the cyanine conjugation provided the active center to concentrate the electronegativity. In conclusion, HDU-108, is expected to be a highly efficient photocatalytic material for environmental remediation.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249996","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}
Piezo-photocatalysis is an effective solution for degrading organic pollutants. In this study, BiSiO nanosheets are successfully synthesized via a one-step hydrothermal method. The piezo-photocatalytic degrading mechanisms of 2,4-Dichlorophenol (2,4-DCP) on BiSiO nanosheets are thoroughly investigated through the integration of experimental study and density functional theory (DFT) calculations. Experimental results revealed outstanding piezoelectric properties for BiSiO nanosheets with a piezoelectric coefficient of 250 pC/N, outperforming previously reported piezo-photocatalysts. The degradation rate constant of 2,4-DCP on BiSiO nanosheets reached 0.0891 min by piezo-photocatalysis, which is 17 and 1.8 times higher than that by solitary photo- and piezo-catalysis, respectively. Furthermore, DFT calculations for BiSiO explain the crucial role of piezoelectric effects in bending its band structure, regulating photogenerated carrier behaviors, and promoting reactive oxygen species (ROS) generation. Finally, the degradation pathways of 2,4-DCP on BiSiO nanosheets were revealed with details. The results of this study offer valuable insights for water treatment with piezo-photocatalysis.
{"title":"Bi2SiO5 nanosheets as piezo-photocatalyst for efficient degradation of 2,4-Dichlorophenol","authors":"Hangyu Shi, Yifu Li, Lishan Zhang, Guoguan Liu, Qian Zhang, Xuan Ru, Shan Zhong","doi":"10.1016/j.apcatb.2024.124581","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124581","url":null,"abstract":"Piezo-photocatalysis is an effective solution for degrading organic pollutants. In this study, BiSiO nanosheets are successfully synthesized via a one-step hydrothermal method. The piezo-photocatalytic degrading mechanisms of 2,4-Dichlorophenol (2,4-DCP) on BiSiO nanosheets are thoroughly investigated through the integration of experimental study and density functional theory (DFT) calculations. Experimental results revealed outstanding piezoelectric properties for BiSiO nanosheets with a piezoelectric coefficient of 250 pC/N, outperforming previously reported piezo-photocatalysts. The degradation rate constant of 2,4-DCP on BiSiO nanosheets reached 0.0891 min by piezo-photocatalysis, which is 17 and 1.8 times higher than that by solitary photo- and piezo-catalysis, respectively. Furthermore, DFT calculations for BiSiO explain the crucial role of piezoelectric effects in bending its band structure, regulating photogenerated carrier behaviors, and promoting reactive oxygen species (ROS) generation. Finally, the degradation pathways of 2,4-DCP on BiSiO nanosheets were revealed with details. The results of this study offer valuable insights for water treatment with piezo-photocatalysis.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249739","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}
Controlling the selective activation of one or some functional groups as desired is still a challenge in hydrogenation, especially at high substrate concentrations. Herein, Pd-MgO interfaces over AlO were finely regulated for efficiently selective hydrogenation of furan ring in 5-hydroxymethylfurfural (HMF) to produce 5-hydroxymethyltetrahydro-2-furaldehyde (5-HMTHFF) or total hydrogenation to 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), also inhibiting side reaction. The Pd-MgO/AlO with 12.0 wt% of MgO selectively hydrogenates the furan rings with a 5-HMTHFF yield of 82.4 % while that with 2.0 wt% of MgO totally hydrogenates HMF with a DHMTHF yield of 96.2 % at high substrate concentrations (400 mM). Characterizations and DFT calculations demonstrated that oligomeric MgO species suppress the agglomeration of Pd nanoparticles and strengthen HMF adsorption, consequently promoting total hydrogenation. Furthermore, Pd-MgO sites between the crystallized MgO and Pd metal favored tilted adsorption on the interface and weakened the activation of the CO bond, consequently selectively producing 5-HMTHFF.
{"title":"Selective switching hydrogenation products of 5-hydroxymethylfurfural at high substrate concentrations by regulating Pd-MgO interactions","authors":"Mingxin Lv, Liyuan Huai, Guoxin Chen, Xi Zhao, Chunlin Chen, Shenghu Zhou, Jian Zhang","doi":"10.1016/j.apcatb.2024.124578","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124578","url":null,"abstract":"Controlling the selective activation of one or some functional groups as desired is still a challenge in hydrogenation, especially at high substrate concentrations. Herein, Pd-MgO interfaces over AlO were finely regulated for efficiently selective hydrogenation of furan ring in 5-hydroxymethylfurfural (HMF) to produce 5-hydroxymethyltetrahydro-2-furaldehyde (5-HMTHFF) or total hydrogenation to 2,5-bis(hydroxymethyl)tetrahydrofuran (BHMTHF), also inhibiting side reaction. The Pd-MgO/AlO with 12.0 wt% of MgO selectively hydrogenates the furan rings with a 5-HMTHFF yield of 82.4 % while that with 2.0 wt% of MgO totally hydrogenates HMF with a DHMTHF yield of 96.2 % at high substrate concentrations (400 mM). Characterizations and DFT calculations demonstrated that oligomeric MgO species suppress the agglomeration of Pd nanoparticles and strengthen HMF adsorption, consequently promoting total hydrogenation. Furthermore, Pd-MgO sites between the crystallized MgO and Pd metal favored tilted adsorption on the interface and weakened the activation of the CO bond, consequently selectively producing 5-HMTHFF.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249998","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 : 2024-09-07DOI: 10.1016/j.apcatb.2024.124582
Bohua Sun, Qianqian Li, Guijin Su, Maoyong Song, Chunyan Ma, Jiaxin Pang, Xu Zhao, Jing Meng, Bin Shi
Sustainable and efficient catalytic oxidation of chlorinated volatile organic compounds (CVOCs) poses an enduring challenge. This bottleneck arises from the limited catalytic activity of redox reactions and chlorine desorption, causing catalyst deactivation and secondary pollution. Herein, our sound strategy involves Ru-loaded facet-engineered {201}-TiO with tuned defects, thereby boosting its reactivity. Comprehensive characterizations and DFT calculation manifested that Ru/{201}-TiO, with abundant oxygen vacancies, Ti defects, and robust metal-support interaction, enabled flexible electron transfer to activate O and the dissociation of HO, thus facilitating the continuous generation of reactive oxygen species (ROS), such as •O and hydroxyl species. These ROS effectively enhance chlorine desorption and chlorobenzene deep oxidation. Ru/{201}-TiO exhibited superior reactivity for chlorobenzene degradation, with an apparent activation energy (Ea) of 31.0 KJ/mol and 100 % chlorobenzene conversion in a 1000-min stability test, even with HO introduction. Ru/{201}-TiO produced 2.2–3.1 times fewer small-molecule chlorinated byproducts than Ru/{101}-TiO, with no polychlorinated benzenes detected.
{"title":"Sustainable and efficient catalytic oxidation of chlorinated volatile organic compounds over Ru-loaded facet-engineered {201}-TiO2 catalyst with tuned defects","authors":"Bohua Sun, Qianqian Li, Guijin Su, Maoyong Song, Chunyan Ma, Jiaxin Pang, Xu Zhao, Jing Meng, Bin Shi","doi":"10.1016/j.apcatb.2024.124582","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124582","url":null,"abstract":"Sustainable and efficient catalytic oxidation of chlorinated volatile organic compounds (CVOCs) poses an enduring challenge. This bottleneck arises from the limited catalytic activity of redox reactions and chlorine desorption, causing catalyst deactivation and secondary pollution. Herein, our sound strategy involves Ru-loaded facet-engineered {201}-TiO with tuned defects, thereby boosting its reactivity. Comprehensive characterizations and DFT calculation manifested that Ru/{201}-TiO, with abundant oxygen vacancies, Ti defects, and robust metal-support interaction, enabled flexible electron transfer to activate O and the dissociation of HO, thus facilitating the continuous generation of reactive oxygen species (ROS), such as •O and hydroxyl species. These ROS effectively enhance chlorine desorption and chlorobenzene deep oxidation. Ru/{201}-TiO exhibited superior reactivity for chlorobenzene degradation, with an apparent activation energy (Ea) of 31.0 KJ/mol and 100 % chlorobenzene conversion in a 1000-min stability test, even with HO introduction. Ru/{201}-TiO produced 2.2–3.1 times fewer small-molecule chlorinated byproducts than Ru/{101}-TiO, with no polychlorinated benzenes detected.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249995","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 : 2024-09-07DOI: 10.1016/j.apcatb.2024.124579
Xiaoling Ren, Honghui Ou, Wei Liu, Yang Lv, Aofei Xu, Zhiwei Ren, Bolun Yang, Guidong Yang
Herein, a new strategy to enhance the nitrogen concentration around the photocatalyst for photocatalytic nitrogen reduction was proposed. And new type of acidic ionic liquid (IL) coupled defective tungsten oxide coated with carbon shell (W@C) was designed and synthesized. The results show that the interaction force between IL and nitrogen is stronger than that between water and nitrogen, which increases the concentration of nitrogen around the tungsten oxide catalyst. In addition, the carbon shell with a hollow structure has a molecular enrichment effect, which can effectively achieve nitrogen enrichment and reduce IL escape. Finally, the ammonia synthesis performance of acidic IL coupled W@C is 52.6 μmol g h, which is about 9 times and 2 times of tungsten oxide and W@C sample, respectively. This work fully reveals the importance of designing the catalyst structure reasonably and increasing the nitrogen concentration around the catalyst to improve the photocatalytic nitrogen reduction performance.
本文提出了一种提高光催化剂周围氮浓度以实现光催化氮还原的新策略。设计并合成了新型酸性离子液体（IL）耦合缺陷氧化钨涂覆碳壳（W@C）。结果表明，离子液体与氮之间的作用力强于水与氮之间的作用力，从而提高了氧化钨催化剂周围的氮浓度。此外，中空结构的碳壳具有分子富集效应，可有效实现氮的富集，减少 IL 的逸出。最后，酸性 IL 耦合 W@C 的氨合成性能为 52.6 μmol g h，分别是氧化钨样品和 W@C 样品的 9 倍和 2 倍左右。这项工作充分揭示了合理设计催化剂结构和提高催化剂周围氮浓度对提高光催化降氮性能的重要性。
{"title":"New Lewis acidic ionic liquid coupled carbon shell coated defective WO3 for efficient photocatalytic N2 reduction","authors":"Xiaoling Ren, Honghui Ou, Wei Liu, Yang Lv, Aofei Xu, Zhiwei Ren, Bolun Yang, Guidong Yang","doi":"10.1016/j.apcatb.2024.124579","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124579","url":null,"abstract":"Herein, a new strategy to enhance the nitrogen concentration around the photocatalyst for photocatalytic nitrogen reduction was proposed. And new type of acidic ionic liquid (IL) coupled defective tungsten oxide coated with carbon shell (W@C) was designed and synthesized. The results show that the interaction force between IL and nitrogen is stronger than that between water and nitrogen, which increases the concentration of nitrogen around the tungsten oxide catalyst. In addition, the carbon shell with a hollow structure has a molecular enrichment effect, which can effectively achieve nitrogen enrichment and reduce IL escape. Finally, the ammonia synthesis performance of acidic IL coupled W@C is 52.6 μmol g h, which is about 9 times and 2 times of tungsten oxide and W@C sample, respectively. This work fully reveals the importance of designing the catalyst structure reasonably and increasing the nitrogen concentration around the catalyst to improve the photocatalytic nitrogen reduction performance.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142250049","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}
Photocatalysis for HO production suffers from low carrier utilization and slow reaction kinetics. Herein, a photocatalytic system supported by a SrCoO-MoS (SCOS) heterojunction, which possessed a unique S-O electron transport channel, was proposed to facilitate HO production under condition where glycerol served as a sacrificial agent. The SCOS heterojunction achieved a remarkable yield of 15.90 mmol g h HO production, 3.7 times higher than the base component SCO. The construction of the heterojunction enriched the oxygen vacancies on the catalyst surface, facilitated photogenerated charge separation, and promoted the adsorption of O, reducing the oxygen reduction reaction (ORR) energy barrier. Besides, glycerol served as a unique proton donor, efficiently captured holes to enhance HO production, and generated valuable by-products including glyceric acid and dihydroxyacetone. Furthermore, SCOS exhibited excellent stability over repeated cycles with consistent HO yields. This study offers an efficient photocatalytic system and demonstrates glycerol’s potential in green oxidation processes.
光催化生产 HO 存在载流子利用率低和反应动力学缓慢的问题。本文提出了一种由 SrCoO-MoS （SCOS）异质结支持的光催化系统，该异质结具有独特的 S-O 电子传输通道，可在甘油作为牺牲剂的条件下促进 HO 的产生。SCOS 异质结的 HO 产率高达 15.90 mmol g h，是基本成分 SCO 产率的 3.7 倍。异质结的构建丰富了催化剂表面的氧空位，促进了光生电荷分离，促进了 O 的吸附，降低了氧还原反应（ORR）的能垒。此外，甘油还是一种独特的质子供体，能有效捕获空穴以提高 HO 的生成，并产生包括甘油酸和二羟基丙酮在内的有价值的副产物。此外，SCOS 在反复循环中表现出卓越的稳定性，并能持续产生 HO。这项研究提供了一种高效的光催化系统，并证明了甘油在绿色氧化过程中的潜力。
{"title":"Efficient photocatalytic H2O2 production and green oxidation of glycerol over a SrCoO3-incorporated catalyst","authors":"Yuxuan He, Yongming Wang, Jin Qian, Kailin Xu, Bianhe Lu, Sijing Tang, Yin Liu, Junwei Shen","doi":"10.1016/j.apcatb.2024.124565","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124565","url":null,"abstract":"Photocatalysis for HO production suffers from low carrier utilization and slow reaction kinetics. Herein, a photocatalytic system supported by a SrCoO-MoS (SCOS) heterojunction, which possessed a unique S-O electron transport channel, was proposed to facilitate HO production under condition where glycerol served as a sacrificial agent. The SCOS heterojunction achieved a remarkable yield of 15.90 mmol g h HO production, 3.7 times higher than the base component SCO. The construction of the heterojunction enriched the oxygen vacancies on the catalyst surface, facilitated photogenerated charge separation, and promoted the adsorption of O, reducing the oxygen reduction reaction (ORR) energy barrier. Besides, glycerol served as a unique proton donor, efficiently captured holes to enhance HO production, and generated valuable by-products including glyceric acid and dihydroxyacetone. Furthermore, SCOS exhibited excellent stability over repeated cycles with consistent HO yields. This study offers an efficient photocatalytic system and demonstrates glycerol’s potential in green oxidation processes.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142249999","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 : 2024-09-05DOI: 10.1016/j.apcatb.2024.124567
Yi Zhao, He Cui, Yidong Hu, Shunli Li, Feng Liu, Boxiong Shen, Kai Ge, Binyuan Liu, Yongfang Yang
A two-dimensional hierarchically porous (2D HP) MOF-Cu layer with a large lateral size was prepared by the amino-groups regulated hydrolysis strategy. The resultant large 2D MOF-Cu layer has many defects owing to the replacement of partial ligands via -OH. 2D HP MOF-Cu large layer showed significantly enhanced photocatalytic activity under full-spectrum irradiation (with the CO production rate about 4.4 times that of the original 3D MOF-Cu sheets). DFT results confirmed that the defective 2D HP MOF-Cu large layer exhibited the new defective state in the valence band, which narrowed the band gap, broadened the light absorption range, promoted the electron transfer, and decreased the Gibbs free energy barrier for COOH* → CO* (about 0.61 eV). This work provides a facile method for the preparation of the defective 2D HP MOFs large layers via the regulation of amino groups from the organic ligands and elucidates the mechanism for improved photocatalytic efficiency.
通过氨基调节水解策略制备了横向尺寸较大的二维分层多孔（2D HP）MOF-Cu 层。由于部分配体被 -OH 取代，因此制备的二维大尺寸 MOF-Cu 层存在许多缺陷。二维 HP MOF-Cu 大层在全光谱辐照下显示出明显增强的光催化活性（CO 生成率约为原始三维 MOF-Cu 片的 4.4 倍）。DFT 结果证实，有缺陷的二维 HP MOF-Cu 大层在价带中表现出新的缺陷态，从而缩小了带隙，拓宽了光吸收范围，促进了电子转移，降低了 COOH* → CO* 的吉布斯自由能垒（约 0.61 eV）。这项工作提供了一种通过调节有机配体中的氨基来制备有缺陷的二维 HP MOFs 大层的简便方法，并阐明了提高光催化效率的机理。
{"title":"A two dimensional hierarchically porous MOF-Cu with large lateral size via amino-groups regulated hydrolysis strategy and its superior photocatalytic reduction of CO2","authors":"Yi Zhao, He Cui, Yidong Hu, Shunli Li, Feng Liu, Boxiong Shen, Kai Ge, Binyuan Liu, Yongfang Yang","doi":"10.1016/j.apcatb.2024.124567","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124567","url":null,"abstract":"A two-dimensional hierarchically porous (2D HP) MOF-Cu layer with a large lateral size was prepared by the amino-groups regulated hydrolysis strategy. The resultant large 2D MOF-Cu layer has many defects owing to the replacement of partial ligands via -OH. 2D HP MOF-Cu large layer showed significantly enhanced photocatalytic activity under full-spectrum irradiation (with the CO production rate about 4.4 times that of the original 3D MOF-Cu sheets). DFT results confirmed that the defective 2D HP MOF-Cu large layer exhibited the new defective state in the valence band, which narrowed the band gap, broadened the light absorption range, promoted the electron transfer, and decreased the Gibbs free energy barrier for COOH* → CO* (about 0.61 eV). This work provides a facile method for the preparation of the defective 2D HP MOFs large layers via the regulation of amino groups from the organic ligands and elucidates the mechanism for improved photocatalytic efficiency.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142226214","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 : 2024-09-05DOI: 10.1016/j.apcatb.2024.124564
Yifei Wang, Yan Du, Peiyang Duan, Beibei Li, Junshan Li, Yongfa Zhu
Controllably steering the photogenerated charge behaviors of semiconductor photocatalysts is crucial in improving photocatalytic oxidation. By engineering the primary facet from (101) to (112), the asymmetrical feather of MIL-101(Fe)(112) result in potential difference on varied facets to contribute to anisotropic charge migration, which has been determined by the preferentially photodeposited cocatalysts on facet (112) and facet (119) of the nanocrystal. Thus-observed anisotropic charge migration of MIL-101(Fe)(112) contribute to 10 times stronger internal electric field (IEF) to accelerate charge separation and migration. Also, we demonstrate the lowest unoccupied crystal orbital (LUCO) of MIL-101(Fe)(112) deepened (up to 3.33 eV vs. NHE) and acquire 3.5 times higher photogenerated holes for robust hole oxidation capacities. As a proof-of-concept, the optimal MIL-101(Fe)(112) can acquire 100 % higher degradation rate and 33 % higher mineralization than MIL-101(Fe)(101). This work highlights the importance of unsymmetric facet manipulation in tailoring photocatalysts for efficient photocatalytic oxidation.
{"title":"Asymmetrical facet-oriented anisotropic charge migration of MIL-101(Fe) with internal electric field-steered photogenerated holes for boosting photocatalytic oxidation","authors":"Yifei Wang, Yan Du, Peiyang Duan, Beibei Li, Junshan Li, Yongfa Zhu","doi":"10.1016/j.apcatb.2024.124564","DOIUrl":"https://doi.org/10.1016/j.apcatb.2024.124564","url":null,"abstract":"Controllably steering the photogenerated charge behaviors of semiconductor photocatalysts is crucial in improving photocatalytic oxidation. By engineering the primary facet from (101) to (112), the asymmetrical feather of MIL-101(Fe)(112) result in potential difference on varied facets to contribute to anisotropic charge migration, which has been determined by the preferentially photodeposited cocatalysts on facet (112) and facet (119) of the nanocrystal. Thus-observed anisotropic charge migration of MIL-101(Fe)(112) contribute to 10 times stronger internal electric field (IEF) to accelerate charge separation and migration. Also, we demonstrate the lowest unoccupied crystal orbital (LUCO) of MIL-101(Fe)(112) deepened (up to 3.33 eV vs. NHE) and acquire 3.5 times higher photogenerated holes for robust hole oxidation capacities. As a proof-of-concept, the optimal MIL-101(Fe)(112) can acquire 100 % higher degradation rate and 33 % higher mineralization than MIL-101(Fe)(101). This work highlights the importance of unsymmetric facet manipulation in tailoring photocatalysts for efficient photocatalytic oxidation.","PeriodicalId":516528,"journal":{"name":"Applied Catalysis B: Environment and Energy","volume":null,"pages":null},"PeriodicalIF":0.0,"publicationDate":"2024-09-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142205081","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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