The oxygen vacancies are significant defects that serve as reactive sites in several catalytic reactions. The CO2 methanation catalysts were facilely designed through tailoring the local electron density on oxygen vacancies by introducing different electron acceptors (Pr, La and Y). We prepared a series of Ni/Ce0.90RE0.10Oδ (RE = rare earth element) catalysts to boost catalytic activity of CO2 methanation at low temperature. It demonstrated the concentration of oxygen vacancies could be significantly regulated by doping strategy, hence altering the local microelectronic structure of catalyst and strengthening the MSI effect. The Ni/Ce0.90Y0.10Oδ catalyst demonstrated the greatest density of oxygen vacancies and optimal CO2 methanation performance. The CO2 conversion and CH4 selectivity achieved 84.6 % and 99.8 % at 270 °C, respectively. In situ DRIFTS revealed Ni/Ce0.90Y0.10Oδ catalyst enhanced the formate pathway. These results can provide better guidance for CO2 utilization technology to develop more efficient catalysts.
{"title":"Boosting the CO2 methanation over Ni/Ce0.90RE0.10Oδ by regulating of oxygen vacancy density","authors":"Jingyi Zhang , Liang Yuan , Yue Li , Yuntao Liang , Lulu Zhou , Yongdong Chen","doi":"10.1016/j.mcat.2025.115040","DOIUrl":"10.1016/j.mcat.2025.115040","url":null,"abstract":"<div><div>The oxygen vacancies are significant defects that serve as reactive sites in several catalytic reactions. The CO<sub>2</sub> methanation catalysts were facilely designed through tailoring the local electron density on oxygen vacancies by introducing different electron acceptors (Pr, La and Y). We prepared a series of Ni/Ce<sub>0.90</sub>RE<sub>0.10</sub>O<sub>δ</sub> (RE = rare earth element) catalysts to boost catalytic activity of CO<sub>2</sub> methanation at low temperature. It demonstrated the concentration of oxygen vacancies could be significantly regulated by doping strategy, hence altering the local microelectronic structure of catalyst and strengthening the MSI effect. The Ni/Ce<sub>0.90</sub>Y<sub>0.10</sub>O<sub>δ</sub> catalyst demonstrated the greatest density of oxygen vacancies and optimal CO<sub>2</sub> methanation performance. The CO<sub>2</sub> conversion and CH<sub>4</sub> selectivity achieved 84.6 % and 99.8 % at 270 °C, respectively. <em>In situ</em> DRIFTS revealed Ni/Ce<sub>0.90</sub>Y<sub>0.10</sub>O<sub>δ</sub> catalyst enhanced the formate pathway. These results can provide better guidance for CO<sub>2</sub> utilization technology to develop more efficient catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115040"},"PeriodicalIF":3.9,"publicationDate":"2025-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143697993","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-25DOI: 10.1016/j.mcat.2025.115054
Ying Yang , Shuo Wang , Yuhang Sun , Jihuan Song , Chenmeng Cui , Sungsik Lee
The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is significant for producing chemicals and fuels from renewable resources, a promising direction in biomass refining. Currently, non-precious metal catalysts suffer from low activity due to a single electronic structure, which is incapable of effectively activating both CO in LA and H2. Herein we report in situ fabricated Co nanoclusters within positive and metallic Co sites on N-doped carbon, which can simultaneously activate LA's CO and H2, enhancing the activity and selectivity for GVL production. Urea-assisted Co dispersion coupled with variation of pyrolysis temperature, Co nanoclusters were formed via direct conversion of Co-containing zinc trimesic acid fibers. The resulting Co nanoclusters possess dual active sites of Co-Nx and metallic Co, with adjustable electronic structures. Under the reaction conditions of 200 °C and 4.5 MPa H2 for 4 h, LA was completely converted, achieving 95 % yield of GVL. The outstanding catalytic activity is attributed to the Co-Nx and metallic Co active sites, which facilitate the activation of CO and H2, respectively. This research provides a new concept for converting N-free metal-organic frameworks into non-precious metal nanoclusters, offering valuable insights for designing high-performance non-precious metal catalysts for biomass-derived chemical and fuel production.
{"title":"Co nanoclusters derived from zinc-trimesic acid fiber for efficient levulinic acid hydrogenation","authors":"Ying Yang , Shuo Wang , Yuhang Sun , Jihuan Song , Chenmeng Cui , Sungsik Lee","doi":"10.1016/j.mcat.2025.115054","DOIUrl":"10.1016/j.mcat.2025.115054","url":null,"abstract":"<div><div>The hydrogenation of levulinic acid (LA) to γ-valerolactone (GVL) is significant for producing chemicals and fuels from renewable resources, a promising direction in biomass refining. Currently, non-precious metal catalysts suffer from low activity due to a single electronic structure, which is incapable of effectively activating both <em>C<img>O</em> in LA and H<sub>2</sub>. Herein we report <em>in situ</em> fabricated Co nanoclusters within positive and metallic Co sites on N-doped carbon, which can simultaneously activate LA's <em>C<img>O</em> and H<sub>2</sub>, enhancing the activity and selectivity for GVL production. Urea-assisted Co dispersion coupled with variation of pyrolysis temperature, Co nanoclusters were formed <em>via</em> direct conversion of Co-containing zinc trimesic acid fibers. The resulting Co nanoclusters possess dual active sites of Co-N<sub>x</sub> and metallic Co, with adjustable electronic structures. Under the reaction conditions of 200 °C and 4.5 MPa H<sub>2</sub> for 4 h, LA was completely converted, achieving 95 % yield of GVL. The outstanding catalytic activity is attributed to the Co-N<sub>x</sub> and metallic Co active sites, which facilitate the activation of <em>C<img>O</em> and H<sub>2</sub>, respectively. This research provides a new concept for converting N-free metal-organic frameworks into non-precious metal nanoclusters, offering valuable insights for designing high-performance non-precious metal catalysts for biomass-derived chemical and fuel production.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115054"},"PeriodicalIF":3.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143697189","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-25DOI: 10.1016/j.mcat.2025.115044
Lizhi Wu, Wenchun Zheng, Xiaofang Wang, Juncheng He, Caixin Zou, Mengjia Zhu, Bo Liu, Li Tan, Yu Tang
Alkali metal promoted Zn/SSZ-13 catalysts were investigated for ethane dehydrogenation (EDH) and CO2-assisted oxidative ethane dehydrogenation (CO2-EDH). The Zn/Na/K/SSZ-13 demonstrated enhanced ethane dehydrogenation performance, achieving 0.381 mol C2H4 gZn-1 h-1 with a low deactivation rate constant of (kd) of 0.04 h-1 in the CO2-EDH process after 440 min time on stream, compared to the unmodified Zn/SSZ-13 catalyst. Comprehensive characterizations revealed that the isolated Zn2+ species serve as the active sites for dehydrogenation, while the addition of alkali metals compensate the acid sites of SSZ-13, effectively suppressing the side reactions such as cracking. Moreover, the introduction of CO2 mitigates Zn loss and enhances catalyst activity and stability by coupling with the reverse water gas shift reaction (RWGS), which also suppress the coke deposition. Investigation of vary CO2 content indicated that higher CO2 concentrations significantly suppress Zn loss and increase the proportion of the RWGS reaction, thereby improving CO2-EDH catalytic performance. This work elucidates the active phase of ethane dehydrogenation and highlights the role of alkali metals and CO2 in the CO2-EDH process over Zn/Na/K/SSZ-13, providing valuable insights for designing high-performance CO2-EDH catalysts.
{"title":"Mechanistic interpretations and insights for the oxidative dehydrogenation of ethane with CO2 over alkali metal modified Zn/SSZ-13 catalyst","authors":"Lizhi Wu, Wenchun Zheng, Xiaofang Wang, Juncheng He, Caixin Zou, Mengjia Zhu, Bo Liu, Li Tan, Yu Tang","doi":"10.1016/j.mcat.2025.115044","DOIUrl":"10.1016/j.mcat.2025.115044","url":null,"abstract":"<div><div>Alkali metal promoted Zn/SSZ-13 catalysts were investigated for ethane dehydrogenation (EDH) and CO<sub>2</sub>-assisted oxidative ethane dehydrogenation (CO<sub>2</sub>-EDH). The Zn/Na/K/SSZ-13 demonstrated enhanced ethane dehydrogenation performance, achieving 0.381 mol C<sub>2</sub>H<sub>4</sub> g<sub>Zn</sub><sup>-1</sup> h<sup>-1</sup> with a low deactivation rate constant of (k<sub>d</sub>) of 0.04 h<sup>-1</sup> in the CO<sub>2</sub>-EDH process after 440 min time on stream, compared to the unmodified Zn/SSZ-13 catalyst. Comprehensive characterizations revealed that the isolated Zn<sup>2+</sup> species serve as the active sites for dehydrogenation, while the addition of alkali metals compensate the acid sites of SSZ-13, effectively suppressing the side reactions such as cracking. Moreover, the introduction of CO<sub>2</sub> mitigates Zn loss and enhances catalyst activity and stability by coupling with the reverse water gas shift reaction (RWGS), which also suppress the coke deposition. Investigation of vary CO<sub>2</sub> content indicated that higher CO<sub>2</sub> concentrations significantly suppress Zn loss and increase the proportion of the RWGS reaction, thereby improving CO<sub>2</sub>-EDH catalytic performance. This work elucidates the active phase of ethane dehydrogenation and highlights the role of alkali metals and CO<sub>2</sub> in the CO<sub>2</sub>-EDH process over Zn/Na/K/SSZ-13, providing valuable insights for designing high-performance CO<sub>2</sub>-EDH catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115044"},"PeriodicalIF":3.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143697992","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The use of fossil fuels leads to environmental issues such as global warming and acid rain. Photocatalytic hydrogen production has become a trend towards solving this problem. However, the rapid recombination of photo-generated electrons and holes in single-component photocatalysts severely limits their photocatalytic performance. Van der Waals (vdW) heterojunctions can effectively suppress the carrier recombination rate. Therefore, this study constructs SnS₂/WTe₂ van der Waals heterojunctions via a vertical stacking approach and employs first-principles calculations to investigate their stability, electronic structure, optical properties, and photocatalytic mechanisms. The results demonstrate that the SnS₂/WTe₂ heterojunction exhibits structural stability, with the valence band maximum (VBM) and conduction band minimum (CBM) dominated by WTe₂ and SnS₂, respectively. The oxidation and reduction potentials of this heterojunction span the redox potential of water, enabling photocatalytic water splitting to proceed normally. Compared to the single-layer materials, the SnS2/WTe2 heterojunction exhibits superior light absorption properties and refractive index. Furthermore, it achieves a hydrogen production efficiency of 9.39 % under AM1.5G solar flux. The application of biaxial strain further optimizes the electronic and optical properties of the SnS₂/WTe₂ heterojunction. The SnS₂/WTe₂ heterojunction exhibits efficient HER and OER performance based on Gibbs free energy calculations. This study provides a highly promising candidate material for the development of high-efficiency hydrogen evolution reaction catalysts.
{"title":"Direct Z-scheme SnS₂/WTe₂ heterojunction for enhanced visible-light-driven water splitting performance based on DFT","authors":"Jie Li, Yongchao Liang, Xiaoxiao Li, Gongmin Wei, Zhihan Zhang, Qian Chen","doi":"10.1016/j.mcat.2025.115048","DOIUrl":"10.1016/j.mcat.2025.115048","url":null,"abstract":"<div><div>The use of fossil fuels leads to environmental issues such as global warming and acid rain. Photocatalytic hydrogen production has become a trend towards solving this problem. However, the rapid recombination of photo-generated electrons and holes in single-component photocatalysts severely limits their photocatalytic performance. Van der Waals (vdW) heterojunctions can effectively suppress the carrier recombination rate. Therefore, this study constructs SnS₂/WTe₂ van der Waals heterojunctions via a vertical stacking approach and employs first-principles calculations to investigate their stability, electronic structure, optical properties, and photocatalytic mechanisms. The results demonstrate that the SnS₂/WTe₂ heterojunction exhibits structural stability, with the valence band maximum (VBM) and conduction band minimum (CBM) dominated by WTe₂ and SnS₂, respectively. The oxidation and reduction potentials of this heterojunction span the redox potential of water, enabling photocatalytic water splitting to proceed normally. Compared to the single-layer materials, the SnS<sub>2</sub>/WTe<sub>2</sub> heterojunction exhibits superior light absorption properties and refractive index. Furthermore, it achieves a hydrogen production efficiency of 9.39 % under AM1.5G solar flux. The application of biaxial strain further optimizes the electronic and optical properties of the SnS₂/WTe₂ heterojunction. The SnS₂/WTe₂ heterojunction exhibits efficient HER and OER performance based on Gibbs free energy calculations. This study provides a highly promising candidate material for the development of high-efficiency hydrogen evolution reaction catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115048"},"PeriodicalIF":3.9,"publicationDate":"2025-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143697191","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-24DOI: 10.1016/j.mcat.2025.115043
Fan Xue, Shangpu Zhuang, Jingyue Bi, Zhaoyang Fei, Xu Qiao
The targeted transformation of biomass resources into premium chemicals and biofuels stands out as a highly promising approach to mitigate greenhouse gas emissions and curb environmental pollution caused by excessive use of fossil fuels. The catalysts with diverse active sites are crucial to determine the products distribution of furan-containing bio-based feedstocks hydrogenation. Herein, Co1/NC and CoNPs/NC catalysts have been successfully prepared and demonstrated distinct reaction pathways in the selective hydrogenation of furfuryl alcohol (FOL). Notably, the Co1/NC catalyst showed 11.8 % FOL conversion within 1 h and both furan ring (C = C) and the C–OH could be hydrogenated over CoN4 sites. In contrast, the Co nanoparticles were more inclined to facilitate the activation and cleavage of C–OH bond in FOL with 92.2 % selectivity of 2-methylfuran and its derivatives over CoNPs/NC catalyst. Although the temperature, H2 pressure and solvents can affect products distribution, their impact differences also depended on the nature of the active sites. This work underscores the importance of a thorough understanding about the structure–activity relationship, which is crucial to systematic design suitable catalysts with tailored active sites for specific catalytic reactions.
{"title":"Distinctive pathways of single-atom and nanoparticle sites over Co-based catalysts for furfuryl alcohol hydrogenation","authors":"Fan Xue, Shangpu Zhuang, Jingyue Bi, Zhaoyang Fei, Xu Qiao","doi":"10.1016/j.mcat.2025.115043","DOIUrl":"10.1016/j.mcat.2025.115043","url":null,"abstract":"<div><div>The targeted transformation of biomass resources into premium chemicals and biofuels stands out as a highly promising approach to mitigate greenhouse gas emissions and curb environmental pollution caused by excessive use of fossil fuels. The catalysts with diverse active sites are crucial to determine the products distribution of furan-containing bio-based feedstocks hydrogenation. Herein, Co<sub>1</sub>/NC and Co<sub>NPs</sub>/NC catalysts have been successfully prepared and demonstrated distinct reaction pathways in the selective hydrogenation of furfuryl alcohol (FOL). Notably, the Co<sub>1</sub>/NC catalyst showed 11.8 % FOL conversion within 1 h and both furan ring (C = C) and the C–OH could be hydrogenated over CoN<sub>4</sub> sites. In contrast, the Co nanoparticles were more inclined to facilitate the activation and cleavage of C–OH bond in FOL with 92.2 % selectivity of 2-methylfuran and its derivatives over Co<sub>NPs</sub>/NC catalyst. Although the temperature, H<sub>2</sub> pressure and solvents can affect products distribution, their impact differences also depended on the nature of the active sites. This work underscores the importance of a thorough understanding about the structure–activity relationship, which is crucial to systematic design suitable catalysts with tailored active sites for specific catalytic reactions.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115043"},"PeriodicalIF":3.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686244","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-24DOI: 10.1016/j.mcat.2025.115034
Jiacheng Fan , Ran Fang , Yanyun Dong , Simeng Qi , Lizi Yang
Density functional theory (DFT) was employed to investigate the reaction mechanisms and stereoselectivity of Ni(II)-catalyzed nonracemic donor-acceptor cyclopropane (DAC) [3 + 2]/[3 + 3] cycloaddition reactions with imine, triazine, and nitrone substrates. The results indicate that the overall reaction for all three substrates consists of two main steps: (1) nucleophilic attack of the substrate on the nonracemic DAC, and (2) C-C cyclization of the resulting key intermediate to form either five- or six-membered rings. For imine and triazine, the most favorable reaction pathway involves direct nucleophilic attack followed by cyclization, while for nitrone, the reaction proceeds via racemization to form an alkene intermediate, which then undergoes cyclization. Computational analysis reveals that the of the diastereoselectivity nucleophilic attack step is primarily controlled by distortion energy, whereas the enantioselectivity of the cyclization step is governed by interaction energy. Global reactivity index (GRI) analysis shows that imine exhibits the highest nucleophilicity with the lowest activation energy, while nitrone displays the weakest nucleophilicity and the highest activation energy. This theoretical study provides new insights into predicting reaction pathways and rationalizing the selective features of related cyclization reactions.
{"title":"Mechanistic insights and stereoselectivity in Ni(II)-catalyzed asymmetric [3 + 2]/[3 + 3] cycloaddition reactions of donor-acceptor cyclopropanes: A DFT study","authors":"Jiacheng Fan , Ran Fang , Yanyun Dong , Simeng Qi , Lizi Yang","doi":"10.1016/j.mcat.2025.115034","DOIUrl":"10.1016/j.mcat.2025.115034","url":null,"abstract":"<div><div>Density functional theory (DFT) was employed to investigate the reaction mechanisms and stereoselectivity of Ni(II)-catalyzed nonracemic donor-acceptor cyclopropane (DAC) [3 + 2]/[3 + 3] cycloaddition reactions with imine, triazine, and nitrone substrates. The results indicate that the overall reaction for all three substrates consists of two main steps: (1) nucleophilic attack of the substrate on the nonracemic DAC, and (2) C-C cyclization of the resulting key intermediate to form either five- or six-membered rings. For imine and triazine, the most favorable reaction pathway involves direct nucleophilic attack followed by cyclization, while for nitrone, the reaction proceeds via racemization to form an alkene intermediate, which then undergoes cyclization. Computational analysis reveals that the of the diastereoselectivity nucleophilic attack step is primarily controlled by distortion energy, whereas the enantioselectivity of the cyclization step is governed by interaction energy. Global reactivity index (GRI) analysis shows that imine exhibits the highest nucleophilicity with the lowest activation energy, while nitrone displays the weakest nucleophilicity and the highest activation energy. This theoretical study provides new insights into predicting reaction pathways and rationalizing the selective features of related cyclization reactions.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115034"},"PeriodicalIF":3.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686243","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-24DOI: 10.1016/j.mcat.2025.115049
Jiaxin Song , Cheng Rao , Zeshu Zhang , Xiangguang Yang , Yibo Zhang
Photocatalytic reforming of plastics, involving converting plastics into valuable chemicals while producing hydrogen from water, is a promising green technology with sustainability potential. However, designing catalysts with optimized structures to further enhance efficiency remained a major challenge. In this study, a series of CdS Quantum dots (QDs) with different sulfur defect concentrations were synthesized by a one-step solvothermal method by adjusting the type of sulfur precursors. In the absence of co-catalysts, the optimal CdS-NS photocatalyst achieved reforming of polyethylene terephthalate (PET) into formate with 870 μmol g−1 h−1 and acetate esters with 90 μmol g−1 h−1, while the hydrogen production rate reached 1771 μmol g−1 h−1. EPR spectra and other analyses confirmed the presence of abundant sulfur defects in the prepared CdS QDs and further demonstrated that the concentration of sulfur defects was closely related to photocatalytic performance. Suitable sulfur defects effectively modulated the electronic and band structure of CdS QDs, enhanced the oxidation capacity of photogenerated holes, reduced the recombination rate of charge carriers, and ultimately improved photocatalytic activity. This work provided an effective approach for designing efficient photocatalysts for the high-value recycling of plastic waste to achieve carbon neutrality.
{"title":"CdS quantum dots with sulfur defects for photoreforming plastics into valuable chemicals coupled with hydrogen production","authors":"Jiaxin Song , Cheng Rao , Zeshu Zhang , Xiangguang Yang , Yibo Zhang","doi":"10.1016/j.mcat.2025.115049","DOIUrl":"10.1016/j.mcat.2025.115049","url":null,"abstract":"<div><div>Photocatalytic reforming of plastics, involving converting plastics into valuable chemicals while producing hydrogen from water, is a promising green technology with sustainability potential. However, designing catalysts with optimized structures to further enhance efficiency remained a major challenge. In this study, a series of CdS Quantum dots (QDs) with different sulfur defect concentrations were synthesized by a one-step solvothermal method by adjusting the type of sulfur precursors. In the absence of co-catalysts, the optimal CdS-NS photocatalyst achieved reforming of polyethylene terephthalate (PET) into formate with 870 μmol <em>g</em><sup>−1</sup> h<sup>−1</sup> and acetate esters with 90 μmol <em>g</em><sup>−1</sup> h<sup>−1</sup>, while the hydrogen production rate reached 1771 μmol <em>g</em><sup>−1</sup> h<sup>−1</sup>. EPR spectra and other analyses confirmed the presence of abundant sulfur defects in the prepared CdS QDs and further demonstrated that the concentration of sulfur defects was closely related to photocatalytic performance. Suitable sulfur defects effectively modulated the electronic and band structure of CdS QDs, enhanced the oxidation capacity of photogenerated holes, reduced the recombination rate of charge carriers, and ultimately improved photocatalytic activity. This work provided an effective approach for designing efficient photocatalysts for the high-value recycling of plastic waste to achieve carbon neutrality.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115049"},"PeriodicalIF":3.9,"publicationDate":"2025-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686812","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The massive emission of dye wastewater has caused significant environmental problems. In this study, zinc-doped titanium dioxide loaded on biochar was synthesized by a simple solvothermal method to investigate its ability of degradation for dyes in photocatalytic process. The discussion focused on the impact of unactivated, acid-activated, and alkali-activated biochar on the properties of composites. Additionally, the composite catalysts underwent comprehensive physical and chemical characterization. The results showed that the particle size of Zn-TiO2OHAC increased significantly, which improved the sedimentation performance. Zn-TiO2OHAC demonstrated exceptional photocatalytic efficiency in the degradation of various pollutants such as Rhodamine B, Congo Red, Methyl Orange, and Methylene Blue. The better performance of the alkali-treated biochar-loaded composite catalysts was attributed to the fact that the alkali-treated biochar changed the electronic structure of the loaded materials and contained more carbon-oxygen functional groups, which was favorable for the separation of electrons and holes.
{"title":"Zn-TiO2/AC photocatalysts for pollutants degradation from experimental and DFT studies","authors":"Xiao Chu, Chen Chen, Ying Liang, Yuliang Chen, Yuliang Wu, Yijiang Liu, Rui Meng, Wenmin Wang, Weiwei Huang, Fei Yang, Xuesong Yi, Jun Cheng","doi":"10.1016/j.mcat.2025.115037","DOIUrl":"10.1016/j.mcat.2025.115037","url":null,"abstract":"<div><div>The massive emission of dye wastewater has caused significant environmental problems. In this study, zinc-doped titanium dioxide loaded on biochar was synthesized by a simple solvothermal method to investigate its ability of degradation for dyes in photocatalytic process. The discussion focused on the impact of unactivated, acid-activated, and alkali-activated biochar on the properties of composites. Additionally, the composite catalysts underwent comprehensive physical and chemical characterization. The results showed that the particle size of Zn-TiO<sub>2<img></sub>OHAC increased significantly, which improved the sedimentation performance. Zn-TiO<sub>2<img></sub>OHAC demonstrated exceptional photocatalytic efficiency in the degradation of various pollutants such as Rhodamine B, Congo Red, Methyl Orange, and Methylene Blue. The better performance of the alkali-treated biochar-loaded composite catalysts was attributed to the fact that the alkali-treated biochar changed the electronic structure of the loaded materials and contained more carbon-oxygen functional groups, which was favorable for the separation of electrons and holes.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115037"},"PeriodicalIF":3.9,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-23DOI: 10.1016/j.mcat.2025.115041
Yu-Song Bi , Cheng-Long Xin , Rong-Zhen Zhang , Hui Liu , Ling-Bao Xing
Exploring the redox window of current photoredox catalysis is a continuous task due to the intrinsic constraints of the technology. In this study, we present a novel supramolecular polymer PDI-CB[8] composed of perylene diimide derivative (PDI) and cucurbit[8]uril (CB[8]) through host-guest interactions, which can stabilize the excited states of PDI* and PDI radical anions (PDI•−), resulting in a highly reducing photocatalytic unit PDI-CB[8]•−* that can efficiently reduce inert sulfoxide to thioether by direct reduction. The supramolecular polymer approach successfully addresses the conventional energy limitations in photoredox catalysis. By exploiting higher-energy excitated illumination of PDI-CB[8], the efficient reduction of unactivated SO double bonds on various substrates was achieved, demonstrating the adaptable usefulness of this method in synthetic chemistry applications.
{"title":"Construction of perylene diimide supramolecular polymers: Study of photocatalytic reduction conversion from sulfoxide to thioether","authors":"Yu-Song Bi , Cheng-Long Xin , Rong-Zhen Zhang , Hui Liu , Ling-Bao Xing","doi":"10.1016/j.mcat.2025.115041","DOIUrl":"10.1016/j.mcat.2025.115041","url":null,"abstract":"<div><div>Exploring the redox window of current photoredox catalysis is a continuous task due to the intrinsic constraints of the technology. In this study, we present a novel supramolecular polymer PDI-CB[8] composed of perylene diimide derivative (PDI) and cucurbit[8]uril (CB[8]) through host-guest interactions, which can stabilize the excited states of PDI* and PDI radical anions (PDI<sup>•−</sup>), resulting in a highly reducing photocatalytic unit PDI-CB[8]<sup>•−*</sup> that can efficiently reduce inert sulfoxide to thioether by direct reduction. The supramolecular polymer approach successfully addresses the conventional energy limitations in photoredox catalysis. By exploiting higher-energy excitated illumination of PDI-CB[8], the efficient reduction of unactivated S<img>O double bonds on various substrates was achieved, demonstrating the adaptable usefulness of this method in synthetic chemistry applications.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115041"},"PeriodicalIF":3.9,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686309","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-03-23DOI: 10.1016/j.mcat.2025.115042
Fen Qiao, Changshun Zheng, Jikang Zhao, Jiaxin Zhou, Genxiang Wang
Aiming at the kinetic bottleneck of hydrogen evolution reaction in hydrogen production by electrolysis of water, Ni(OH)2-TiO2 composites were successfully prepared on nickel foam (NF) substrate by two-step hydrothermal method. By adjusting the concentration of nickel source and reaction conditions, the composite catalysts with excellent morphology and structure were constructed. The Ni(OH)2-TiO2 catalyst prepared under the optimized conditions has an overpotential of only 63 mV at the current density of 10 mA·cm−2, showing lower Tafel slope, higher double layer capacitance and excellent reaction kinetics. The results of density functional theory (DFT) revealed the phenomenon of charge transfer inside the composite and the influence of interface effect on the electron structure, and further confirmed that the electrons transfer from Ni(OH)2 to TiO2 optimized the charge distribution inside the composite, promoted the charge transfer at the interface, and reduced the activation energy of catalytic reaction.
{"title":"Morphology control of Ni(OH)2-TiO2 nanosheet array and its excellent electrochemical hydrogen evolution performance","authors":"Fen Qiao, Changshun Zheng, Jikang Zhao, Jiaxin Zhou, Genxiang Wang","doi":"10.1016/j.mcat.2025.115042","DOIUrl":"10.1016/j.mcat.2025.115042","url":null,"abstract":"<div><div>Aiming at the kinetic bottleneck of hydrogen evolution reaction in hydrogen production by electrolysis of water, Ni(OH)<sub>2</sub>-TiO<sub>2</sub> composites were successfully prepared on nickel foam (NF) substrate by two-step hydrothermal method. By adjusting the concentration of nickel source and reaction conditions, the composite catalysts with excellent morphology and structure were constructed. The Ni(OH)<sub>2</sub>-TiO<sub>2</sub> catalyst prepared under the optimized conditions has an overpotential of only 63 mV at the current density of 10 mA·cm<sup>−2</sup>, showing lower Tafel slope, higher double layer capacitance and excellent reaction kinetics. The results of density functional theory (DFT) revealed the phenomenon of charge transfer inside the composite and the influence of interface effect on the electron structure, and further confirmed that the electrons transfer from Ni(OH)<sub>2</sub> to TiO<sub>2</sub> optimized the charge distribution inside the composite, promoted the charge transfer at the interface, and reduced the activation energy of catalytic reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115042"},"PeriodicalIF":3.9,"publicationDate":"2025-03-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143686310","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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