Pub Date : 2025-11-04DOI: 10.1016/j.apcata.2025.120672
Lingxin Meng , Shaowen Wu , Yuteng Jia , Haojun Sun , Fuda Chen , Junxin Lan
Dry reforming of methane (DRM) is an effective way to convert two greenhouse gases into fuels. However, high energy consumption and catalyst deactivation restrict its development. Here, Ni/MgAl2O4 and Ni/Al2O3 were prepared for thermal catalytic and photothermal catalytic DRM, and their reaction mechanisms were explored. 1Ni/MgAl2O4 exhibits excellent thermal catalytic activity and stability, while 1Ni/Al2O3 gradually deactivates after the initial 6 h of stability due to the coating of Ni nanoparticles with Al2O3. In-situ DRIFTS confirmed that 1Ni/MgAl2O4 and 1Ni/Al2O3 followed reaction mechanisms of E-R and L-H, respectively. In addition, under focused UV–VIS–IR irradiation, extremely high fuel yield value (91.18 and 100.80 mmol g−1 min−1 for pH2 and pCO) and excellent stability (60 h) achieved. The outstanding performance is attributed to efficient solar-thermal conversion, which provides the necessary heat for the reaction, coupled with molecular activation effect that further reduced the apparent activation energy.
{"title":"Efficient photothermal catalysis of dry reforming of methane over Ni/MgAl2O4: A full-spectrum solar utilization strategy","authors":"Lingxin Meng , Shaowen Wu , Yuteng Jia , Haojun Sun , Fuda Chen , Junxin Lan","doi":"10.1016/j.apcata.2025.120672","DOIUrl":"10.1016/j.apcata.2025.120672","url":null,"abstract":"<div><div>Dry reforming of methane (DRM) is an effective way to convert two greenhouse gases into fuels. However, high energy consumption and catalyst deactivation restrict its development. Here, Ni/MgAl<sub>2</sub>O<sub>4</sub> and Ni/Al<sub>2</sub>O<sub>3</sub> were prepared for thermal catalytic and photothermal catalytic DRM, and their reaction mechanisms were explored. 1Ni/MgAl<sub>2</sub>O<sub>4</sub> exhibits excellent thermal catalytic activity and stability, while 1Ni/Al<sub>2</sub>O<sub>3</sub> gradually deactivates after the initial 6 h of stability due to the coating of Ni nanoparticles with Al<sub>2</sub>O<sub>3</sub>. In-situ DRIFTS confirmed that 1Ni/MgAl<sub>2</sub>O<sub>4</sub> and 1Ni/Al<sub>2</sub>O<sub>3</sub> followed reaction mechanisms of E-R and L-H, respectively. In addition, under focused UV–VIS–IR irradiation, extremely high fuel yield value (91.18 and 100.80 mmol g<sup>−1</sup> min<sup>−1</sup> for p<sub>H2</sub> and p<sub>CO</sub>) and excellent stability (60 h) achieved. The outstanding performance is attributed to efficient solar-thermal conversion, which provides the necessary heat for the reaction, coupled with molecular activation effect that further reduced the apparent activation energy.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"710 ","pages":"Article 120672"},"PeriodicalIF":4.8,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145448483","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 : 2025-11-04DOI: 10.1016/j.apcata.2025.120671
Sijie Lin , De-Kun Ma , Hehe Zhou , Haifeng Yuan , Cong Wan , Xia Hu
Photocatalytic activity of pristine resorcinol formalde (RF) resin in hydrogen peroxide production is still unsatisfying for practical application because of poor separation efficiency of photogenerated carriers. Contact electrification (CE) between polytetrafluoroehtylene (PTFE) and water (H2O) can not only generate hydrogen peroxide (H2O2) but also form a strong interfacial electrostatic field (IEF). However, whether the IEF can be used to promote the separation of photogenerated carriers of the photocatalysts is still unclear. Herein, taking RF resin as a model photocatalyst, we have synthesized RF resin/PTFE photocatalytic/contact-electro-catalytic composite catalysts and further demonstrated that the IEF formed between PTFE and H2O could be used to facilitate the separation of photogenerated carriers of the RF resins. As a result, H2O2 production rate reached 56.5 µmol·h−1 over RF/PTFE under simultaneous visible light irradiation and ultrasonication, which is 33-times and 2-times higher than those obtained on individual PTFE (1.7 µmol·h−1) and RF (28.1 µmol·h−1). CE could also enhance H2O2 generation rate of other photocatalysts, showing its generality. Not only that, RF/PTFE could be used to fabricate CE-photocatalysis-self-Fenton system for environmental purification.
{"title":"Enhanced hydrogen peroxide photosynthesis achieved over resorcinol formalde resin/polytetrafluoroehtylene through contact electrification","authors":"Sijie Lin , De-Kun Ma , Hehe Zhou , Haifeng Yuan , Cong Wan , Xia Hu","doi":"10.1016/j.apcata.2025.120671","DOIUrl":"10.1016/j.apcata.2025.120671","url":null,"abstract":"<div><div>Photocatalytic activity of pristine resorcinol formalde (RF) resin in hydrogen peroxide production is still unsatisfying for practical application because of poor separation efficiency of photogenerated carriers. Contact electrification (CE) between polytetrafluoroehtylene (PTFE) and water (H<sub>2</sub>O) can not only generate hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) but also form a strong interfacial electrostatic field (IEF). However, whether the IEF can be used to promote the separation of photogenerated carriers of the photocatalysts is still unclear. Herein, taking RF resin as a model photocatalyst, we have synthesized RF resin/PTFE photocatalytic/contact-electro-catalytic composite catalysts and further demonstrated that the IEF formed between PTFE and H<sub>2</sub>O could be used to facilitate the separation of photogenerated carriers of the RF resins. As a result, H<sub>2</sub>O<sub>2</sub> production rate reached 56.5 µmol·h<sup>−1</sup> over RF/PTFE under simultaneous visible light irradiation and ultrasonication, which is 33-times and 2-times higher than those obtained on individual PTFE (1.7 µmol·h<sup>−1</sup>) and RF (28.1 µmol·h<sup>−1</sup>). CE could also enhance H<sub>2</sub>O<sub>2</sub> generation rate of other photocatalysts, showing its generality. Not only that, RF/PTFE could be used to fabricate CE-photocatalysis-self-Fenton system for environmental purification.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"709 ","pages":"Article 120671"},"PeriodicalIF":4.8,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145462693","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 : 2025-11-04DOI: 10.1016/j.apcata.2025.120673
Yonggang Lei , Yongchun Tong , Qingyun Wang , Yuqi Han , Xiaojuan Feng , Zhen Li , Shoubo Li , Kim Hoong Ng
A well-engineered heterojunction cocatalysts play a pivotal role in enabling efficient H2 evolution over semiconductor materials. Herein, an effective cocatalyst derived from MoP/Mo2N heterostructure was proposed and incorporated to CdS for a drastically enhanced H2 production from water under visible light irradiation. By optimizing catalytic formulation, the best-performing CdS@MoP/Mo2N(3 wt%) demonstrates a remarkable H2 production rate of 10653 μmol h⁻¹g⁻¹ , representing an 18-fold enhancement compared to bare CdS. This remarkably high activity outperforms CdS enhanced by conventional noble metal cocatalysts (e.g., Ag, Au, Pt) and MoSx-based materials, underscoring the outstanding cocatalytic effect promised by MoP/Mo2N. In parallel, the optimized photocatalyst also achieved a remarkable stability for H2 production over 9 consecutive cycles with a total irradiation time of 45 h, alongside a noticeably high apparent quantum efficiency (AQE) of 13.5 % upon irradiated by 420 nm-light. According to analysis, these enhanced performances are ascribed to the promoted interfacial charge transfer kinetics and significantly reduced hydrogen evolution overpotential of CdS@MoP/Mo2N(3 wt%), both of which contribute to the superior catalytic activity. Theoretical investigation also suggested a much-facilitated electron shuttling and proton desorption with MoP/Mo2N attached to CdS photocatalyst. Overall, this work demonstrates that our developed MoP/Mo2N heterostructure cocatalysts can effectively serve as alternatives to noble metals(Ag, Au, Pt) in solar-driven photocatalytic hydrogen production.
{"title":"Unraveling the role of MoP/Mo2N heterojunctions in enhancing the photocatalytic hydrogen evolution activity of CdS","authors":"Yonggang Lei , Yongchun Tong , Qingyun Wang , Yuqi Han , Xiaojuan Feng , Zhen Li , Shoubo Li , Kim Hoong Ng","doi":"10.1016/j.apcata.2025.120673","DOIUrl":"10.1016/j.apcata.2025.120673","url":null,"abstract":"<div><div>A well-engineered heterojunction cocatalysts play a pivotal role in enabling efficient H<sub>2</sub> evolution over semiconductor materials. Herein, an effective cocatalyst derived from MoP/Mo<sub>2</sub>N heterostructure was proposed and incorporated to CdS for a drastically enhanced H<sub>2</sub> production from water under visible light irradiation. By optimizing catalytic formulation, the best-performing CdS@MoP/Mo<sub>2</sub>N(3 wt%) demonstrates a remarkable H<sub>2</sub> production rate of 10653 μmol h⁻¹g⁻¹ , representing an 18-fold enhancement compared to bare CdS. This remarkably high activity outperforms CdS enhanced by conventional noble metal cocatalysts (e.g., Ag, Au, Pt) and MoS<sub>x</sub>-based materials, underscoring the outstanding cocatalytic effect promised by MoP/Mo<sub>2</sub>N. In parallel, the optimized photocatalyst also achieved a remarkable stability for H<sub>2</sub> production over 9 consecutive cycles with a total irradiation time of 45 h, alongside a noticeably high apparent quantum efficiency (AQE) of 13.5 % upon irradiated by 420 nm-light. According to analysis, these enhanced performances are ascribed to the promoted interfacial charge transfer kinetics and significantly reduced hydrogen evolution overpotential of CdS@MoP/Mo<sub>2</sub>N(3 wt%), both of which contribute to the superior catalytic activity. Theoretical investigation also suggested a much-facilitated electron shuttling and proton desorption with MoP/Mo<sub>2</sub>N attached to CdS photocatalyst. Overall, this work demonstrates that our developed MoP/Mo<sub>2</sub>N heterostructure cocatalysts can effectively serve as alternatives to noble metals(Ag, Au, Pt) in solar-driven photocatalytic hydrogen production.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"710 ","pages":"Article 120673"},"PeriodicalIF":4.8,"publicationDate":"2025-11-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464900","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 : 2025-11-01DOI: 10.1016/j.apcata.2025.120667
Yujing Li , Yanxia Wang , Wei Liu , Lingmin Sun , Tengfei Guo , Jiangshan Zhao , Danyang Li , Xiang Li , Zhigang Wang
Lignin, as the most abundant renewable aromatic polymer in nature, is a key resource for sustainable biorefining and the production of value-added chemicals. Electrocatalytic lignin depolymerization has emerged as a promising approach for the valorization of lignin due to its mild conditions, tunable reactivity, and high energy efficiency. This review systematically summarizes recent advances in the rational design and development of electrocatalysts, covering noble metals, non-noble metal compounds, as well as innovative molecular and biomimetic catalysts, with a focus on reaction mechanisms and structure–performance relationships. Key design strategies such as single-atom dispersion, support engineering, defect modulation, and tandem catalysis are discussed in depth for enhancing catalytic activity, selectivity, and stability, highlighting the critical role of electronic structure modulation in substrate adsorption and conversion. This review further dissects the fundamental mechanisms of electrocatalytic oxidation and hydrogenolysis, while also assessing pioneering progress in electrolyte and reactor design from a systems perspective. The discussion culminates in a critical outlook on current challenges and a forward-looking roadmap for achieving sustainable industrial application.
{"title":"Progress and prospects of catalysts for electrocatalytic lignin depolymerization","authors":"Yujing Li , Yanxia Wang , Wei Liu , Lingmin Sun , Tengfei Guo , Jiangshan Zhao , Danyang Li , Xiang Li , Zhigang Wang","doi":"10.1016/j.apcata.2025.120667","DOIUrl":"10.1016/j.apcata.2025.120667","url":null,"abstract":"<div><div>Lignin, as the most abundant renewable aromatic polymer in nature, is a key resource for sustainable biorefining and the production of value-added chemicals. Electrocatalytic lignin depolymerization has emerged as a promising approach for the valorization of lignin due to its mild conditions, tunable reactivity, and high energy efficiency. This review systematically summarizes recent advances in the rational design and development of electrocatalysts, covering noble metals, non-noble metal compounds, as well as innovative molecular and biomimetic catalysts, with a focus on reaction mechanisms and structure–performance relationships. Key design strategies such as single-atom dispersion, support engineering, defect modulation, and tandem catalysis are discussed in depth for enhancing catalytic activity, selectivity, and stability, highlighting the critical role of electronic structure modulation in substrate adsorption and conversion. This review further dissects the fundamental mechanisms of electrocatalytic oxidation and hydrogenolysis, while also assessing pioneering progress in electrolyte and reactor design from a systems perspective. The discussion culminates in a critical outlook on current challenges and a forward-looking roadmap for achieving sustainable industrial application.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"710 ","pages":"Article 120667"},"PeriodicalIF":4.8,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145464918","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 : 2025-11-01DOI: 10.1016/j.apcata.2025.120669
Xin Han , Shanguang Xu , Fan Zhang , Ruiying Chai , Shanguo Du , Xiuling Jiao , Dairong Chen , Jie Zhang
Bimetallic catalysts composed of a primary hydrogenation metal with an oxyphilic metal often exhibit superior catalytic performance compared to their single-metal counterparts. This study elucidates the bimetallic synergy of cobalt-modified MgO-supported Pt catalysts for promoting the selective hydrodeoxygenation of guaiacol to cyclohexanol. The incorporation of Co significantly enhanced both the activity and cyclohexanol selectivity of the Pt/MgO catalyst, with performance following a volcanic trend relative to Co content. The optimal catalyst, Pt-15Co/MgO, exhibited remarkable performance, achieving 98 % guaiacol conversion and 96 % cyclohexanol selectivity at 180 °C and 1 MPa H2 pressure. The addition of Co effectively suppressed the growth of Pt particles and improved Pt dispersion. Moreover, Co modification could induce the electron transfer from Co to Pt and promote the reduction of Pt species, leading to the formation of more active Pt0 sites beneficial for hydrogen activation. The presence of oxyphilic Co also could promote the adsorption of the guaiacol molecules and enhance hydrogen spillover. Pt and Co exhibited a distinct synergistic effect in the hydrodeoxygenation process: Co sites primarily promoted C–O bond cleavage, while Pt sites facilitated hydrogen activation. This complementary cooperation altered the reaction pathway, lowered the activation energy, and thereby improved the catalytic performance. These findings offer a rational strategy for designing highly efficient bimetallic catalysts and provide theoretical guidance for the catalytic conversion of lignin-derived oxygenates.
{"title":"Bimetallic synergy in the PtCo/MgO catalysts for promoting hydrodeoxygenation of guaiacol to cyclohexanol","authors":"Xin Han , Shanguang Xu , Fan Zhang , Ruiying Chai , Shanguo Du , Xiuling Jiao , Dairong Chen , Jie Zhang","doi":"10.1016/j.apcata.2025.120669","DOIUrl":"10.1016/j.apcata.2025.120669","url":null,"abstract":"<div><div>Bimetallic catalysts composed of a primary hydrogenation metal with an oxyphilic metal often exhibit superior catalytic performance compared to their single-metal counterparts. This study elucidates the bimetallic synergy of cobalt-modified MgO-supported Pt catalysts for promoting the selective hydrodeoxygenation of guaiacol to cyclohexanol. The incorporation of Co significantly enhanced both the activity and cyclohexanol selectivity of the Pt/MgO catalyst, with performance following a volcanic trend relative to Co content. The optimal catalyst, Pt-15Co/MgO, exhibited remarkable performance, achieving 98 % guaiacol conversion and 96 % cyclohexanol selectivity at 180 °C and 1 MPa H<sub>2</sub> pressure. The addition of Co effectively suppressed the growth of Pt particles and improved Pt dispersion. Moreover, Co modification could induce the electron transfer from Co to Pt and promote the reduction of Pt species, leading to the formation of more active Pt<sup>0</sup> sites beneficial for hydrogen activation. The presence of oxyphilic Co also could promote the adsorption of the guaiacol molecules and enhance hydrogen spillover. Pt and Co exhibited a distinct synergistic effect in the hydrodeoxygenation process: Co sites primarily promoted C–O bond cleavage, while Pt sites facilitated hydrogen activation. This complementary cooperation altered the reaction pathway, lowered the activation energy, and thereby improved the catalytic performance. These findings offer a rational strategy for designing highly efficient bimetallic catalysts and provide theoretical guidance for the catalytic conversion of lignin-derived oxygenates.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"709 ","pages":"Article 120669"},"PeriodicalIF":4.8,"publicationDate":"2025-11-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145462694","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 : 2025-10-31DOI: 10.1016/j.apcata.2025.120668
Zhenhui Huang , Xiangying Wang , Wei Na , Xinyu Ling , Xingpeng Sun , Runqin Chen , Wengui Gao , Hua Wang
The surface properties of catalysts play a crucial role in CO2 hydrogenation. In this study, Cu-loaded Ce–Zr oxide (CCZ) catalysts with distinct activities were synthesized via four methods. Catalytic testing revealed that the CCZ-HM catalyst exhibited the highest performance, achieving the greatest methanol space–time yield (STY). Structural and surface analyses revealed that low-valence Cu specie, oxygen vacancies, strong metal–support interactions, and balanced acid–base properties contributed to enhanced catalytic performance of the CCZ catalysts. Mechanistic studies indicated that CCZ-CP and CCZ-HM catalysts exhibited higher oxygen vacancy concentrations and enhanced surface acidity-basicity, which promoted CO₂ adsorption and the formation of carbonate species. In a CO2 + H2 atmosphere, both catalysts mainly formed bidentate formate species, which served as key intermediates in methanol synthesis. However, the strong adsorption capacity and limited H2 spillover of the CCZ-CP catalyst hindered further hydrogenation of these intermediates, thereby reducing methanol production. In contrast, the excellent acid–base synergy and efficient H₂ spillover of CCZ-HM promoted the hydrogenation of CO₂-derived intermediates to methanol, resulting in enhanced STY. These findings indicate that the rational control of catalyst surface acidity, oxygen vacancy concentration, and H2 activation ability is crucial for improving overall catalyst performance.
{"title":"Influence of catalyst surface properties on product selectivity in CO2 hydrogenation over Cu–Ce–Zr oxide solid solutions","authors":"Zhenhui Huang , Xiangying Wang , Wei Na , Xinyu Ling , Xingpeng Sun , Runqin Chen , Wengui Gao , Hua Wang","doi":"10.1016/j.apcata.2025.120668","DOIUrl":"10.1016/j.apcata.2025.120668","url":null,"abstract":"<div><div>The surface properties of catalysts play a crucial role in CO<sub>2</sub> hydrogenation. In this study, Cu-loaded Ce–Zr oxide (CCZ) catalysts with distinct activities were synthesized via four methods. Catalytic testing revealed that the CCZ-HM catalyst exhibited the highest performance, achieving the greatest methanol space–time yield (STY). Structural and surface analyses revealed that low-valence Cu specie, oxygen vacancies, strong metal–support interactions, and balanced acid–base properties contributed to enhanced catalytic performance of the CCZ catalysts. Mechanistic studies indicated that CCZ-CP and CCZ-HM catalysts exhibited higher oxygen vacancy concentrations and enhanced surface acidity-basicity, which promoted CO₂ adsorption and the formation of carbonate species. In a CO<sub>2</sub> + H<sub>2</sub> atmosphere, both catalysts mainly formed bidentate formate species, which served as key intermediates in methanol synthesis. However, the strong adsorption capacity and limited H<sub>2</sub> spillover of the CCZ-CP catalyst hindered further hydrogenation of these intermediates, thereby reducing methanol production. In contrast, the excellent acid–base synergy and efficient H₂ spillover of CCZ-HM promoted the hydrogenation of CO₂-derived intermediates to methanol, resulting in enhanced STY. These findings indicate that the rational control of catalyst surface acidity, oxygen vacancy concentration, and H<sub>2</sub> activation ability is crucial for improving overall catalyst performance.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"709 ","pages":"Article 120668"},"PeriodicalIF":4.8,"publicationDate":"2025-10-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463381","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 : 2025-10-30DOI: 10.1016/j.apcata.2025.120665
Yongjun Liu , Fei Wang , Xiaoshuang Wang , Chaoyu Zhang , Shiqi Tao , Jialiang Sun , Chuanmin Li , Haijun Guo , Wei Huang
Currently, the direct partial oxidation of methane mainly focused on producing C1 oxygenates in a batch reactor, while continuous converting methane to C2+oxygenates is attractive but challenged by C-C coupling at low temperature. Herein, we developed a continuous trickle bed reactor for acetic acid production from CH4-CO mixtures using a Fe/ZSM-5 catalyst at 50 °C. The Fe0.1/ZSM-5 catalyst with Fe loading of 0.1 wt.% exhibits superior acetic acid yield of 311.5 µmol·gcat−1·h−1 and excellent stability. The enhanced acetic acid yield is associated with the synergy between mononuclear Fe species and the Brønsted acid sites. Control experiments and in-situ DRIFTS spectroscopy unveil a CH3O-mediated tandem carbonylation pathway: H2O2-assisted CH4 dehydrogenation occurs on mononuclear Fe sites to generate CH3O*intermediate, followed by CO carbonylation on Brønsted acid sites and further protonation to achieve acetic acid. This work reveals a new pathway for acetic acid formation and provides a new continuous technique to produce it from CH4 under mild conditions, as well as offering a sustainable route for upgrading natural gas and Fischer-Tropsch tail gases.
{"title":"Synergistic Fe sites and Brønsted acid in Fe/ZSM-5 for methane to acetic acid using a continuous trickle-bed reactor at low-temperature","authors":"Yongjun Liu , Fei Wang , Xiaoshuang Wang , Chaoyu Zhang , Shiqi Tao , Jialiang Sun , Chuanmin Li , Haijun Guo , Wei Huang","doi":"10.1016/j.apcata.2025.120665","DOIUrl":"10.1016/j.apcata.2025.120665","url":null,"abstract":"<div><div>Currently, the direct partial oxidation of methane mainly focused on producing C1 oxygenates in a batch reactor, while continuous converting methane to C<sub>2+</sub>oxygenates is attractive but challenged by C-C coupling at low temperature. Herein, we developed a continuous trickle bed reactor for acetic acid production from CH<sub>4</sub>-CO mixtures using a Fe/ZSM-5 catalyst at 50 °C. The Fe<sub>0.1</sub>/ZSM-5 catalyst with Fe loading of 0.1 <em>wt.</em>% exhibits superior acetic acid yield of 311.5 µmol·g<sub>cat</sub><sup>−1</sup>·h<sup>−1</sup> and excellent stability. The enhanced acetic acid yield is associated with the synergy between mononuclear Fe species and the Brønsted acid sites. Control experiments and <em>in-situ</em> DRIFTS spectroscopy unveil a CH<sub>3</sub>O-mediated tandem carbonylation pathway: H<sub>2</sub>O<sub>2</sub>-assisted CH<sub>4</sub> dehydrogenation occurs on mononuclear Fe sites to generate CH<sub>3</sub>O*intermediate, followed by CO carbonylation on Brønsted acid sites and further protonation to achieve acetic acid. This work reveals a new pathway for acetic acid formation and provides a new continuous technique to produce it from CH<sub>4</sub> under mild conditions, as well as offering a sustainable route for upgrading natural gas and Fischer-Tropsch tail gases.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"709 ","pages":"Article 120665"},"PeriodicalIF":4.8,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463334","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 : 2025-10-30DOI: 10.1016/j.apcata.2025.120666
Tingcong Wang , Ming Lu , Yusheng Lu , Bin Dai , Mingyuan Zhu
Sn-based catalysts are considered as one of the alternatives to the toxic mercury catalysts for acetylene hydrochlorination. However, the wide application of Sn-based catalysts was limited due to their poor stability. Herein, high-density Sn single-atom catalysts were synthesized with chitosan and SnCl2 as precursors, and the controlled structures were achieved by adjusting the calcination process. The obtained SnCS-600 catalyst displayed an acetylene conversion of 99.05 % at 180 °C and GHSV(C2H2) = 90 h−1, and the acetylene conversion remained higher than 70 % after continuous operation for 150 h. Sn atoms and pyridine N were the active sites of acetylene hydrochlorination, which adsorbed HCl and C2H2, respectively. The excellent stability of SnCS-600 was attributed to the strong interaction between N and Sn atoms, which inhibited the loss of Sn in acetylene hydrochlorination. This work provided new strategies for preparing Sn-based catalysts as mercury-free catalysts.
{"title":"High-density single-atom tin catalyst catalyzes the hydrochlorination of acetylene","authors":"Tingcong Wang , Ming Lu , Yusheng Lu , Bin Dai , Mingyuan Zhu","doi":"10.1016/j.apcata.2025.120666","DOIUrl":"10.1016/j.apcata.2025.120666","url":null,"abstract":"<div><div>Sn-based catalysts are considered as one of the alternatives to the toxic mercury catalysts for acetylene hydrochlorination. However, the wide application of Sn-based catalysts was limited due to their poor stability. Herein, high-density Sn single-atom catalysts were synthesized with chitosan and SnCl<sub>2</sub> as precursors, and the controlled structures were achieved by adjusting the calcination process. The obtained SnCS-600 catalyst displayed an acetylene conversion of 99.05 % at 180 °C and GHSV(C<sub>2</sub>H<sub>2</sub>) = 90 h<sup>−1</sup>, and the acetylene conversion remained higher than 70 % after continuous operation for 150 h. Sn atoms and pyridine N were the active sites of acetylene hydrochlorination, which adsorbed HCl and C<sub>2</sub>H<sub>2</sub>, respectively. The excellent stability of SnCS-600 was attributed to the strong interaction between N and Sn atoms, which inhibited the loss of Sn in acetylene hydrochlorination. This work provided new strategies for preparing Sn-based catalysts as mercury-free catalysts.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"709 ","pages":"Article 120666"},"PeriodicalIF":4.8,"publicationDate":"2025-10-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145413384","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}
NH3 cracking is receiving growing attention for the exploitation of ammonia as H2 carrier. Of the different aspects of this process that require in depth study, the choice of the optimal catalyst is arguably one of the most important, being the process kinetically controlled. Literature agrees that ruthenium is the most active metal for low temperature ammonia cracking, however, no consensus on the kinetic expression has been reached due to the high sensitivity of the reaction mechanism to the specific reaction conditions. For this reason, it is of utmost importance to work in conditions as close as possible to the industrial ones to derive a reaction rate useful for practical reactor design. This is challenging due to the strong endothermicity of the reaction that leads to non-uniform temperature profiles in concentrated kinetic tests, and the impact of temperature gradients in kinetic studies is well known in the literature. In this study, the activity of a commercial Ru/Al2O3 catalyst in the form of small spherical particles was investigated by feeding pure ammonia in the 2500–20’000 Ncc/h/gcat range at up to 3 bar-a as well as by cofeeding reaction products. Despite working with undiluted catalyst and pure ammonia in an integral reactor up to ≅ 100 % NH3 conversions, the inclusion of a thermally conductive aluminium POCS reactor internal enabled to achieve almost isothermal conditions, resulting in a LHHW rate expression able to fit the whole experimental data set with a MPE less than 5 %.
{"title":"Investigation of the ammonia cracking kinetics over Ru/Al2O3 using conductive reactor internals","authors":"Federico Sascha Franchi, Matteo Ambrosetti, Nicola Usberti, Alessandra Beretta, Gianpiero Groppi, Enrico Tronconi","doi":"10.1016/j.apcata.2025.120664","DOIUrl":"10.1016/j.apcata.2025.120664","url":null,"abstract":"<div><div>NH<sub>3</sub> cracking is receiving growing attention for the exploitation of ammonia as H<sub>2</sub> carrier. Of the different aspects of this process that require in depth study, the choice of the optimal catalyst is arguably one of the most important, being the process kinetically controlled. Literature agrees that ruthenium is the most active metal for low temperature ammonia cracking, however, no consensus on the kinetic expression has been reached due to the high sensitivity of the reaction mechanism to the specific reaction conditions. For this reason, it is of utmost importance to work in conditions as close as possible to the industrial ones to derive a reaction rate useful for practical reactor design. This is challenging due to the strong endothermicity of the reaction that leads to non-uniform temperature profiles in concentrated kinetic tests, and the impact of temperature gradients in kinetic studies is well known in the literature. In this study, the activity of a commercial Ru/Al<sub>2</sub>O<sub>3</sub> catalyst in the form of small spherical particles was investigated by feeding pure ammonia in the 2500–20’000 Ncc/h/g<sub>cat</sub> range at up to 3 bar-a as well as by cofeeding reaction products. Despite working with undiluted catalyst and pure ammonia in an integral reactor up to ≅ 100 % NH<sub>3</sub> conversions, the inclusion of a thermally conductive aluminium POCS reactor internal enabled to achieve almost isothermal conditions, resulting in a LHHW rate expression able to fit the whole experimental data set with a MPE less than 5 %.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"709 ","pages":"Article 120664"},"PeriodicalIF":4.8,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145463333","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 photocatalytic production of H2O2 from H2O and O2via solar light-driven is a low-cost, safe, and environmentally friendly route for H2O2 production, but the high carrier recombination rate and insufficient active sites in the photocatalytic process greatly limit the efficiency of H2O2 generation. Here, we combined both vacancy modification and heterojunction engineering strategies to modify In2S3, successfully constructing In2S3/Ni Schottky junctions (SvIS/Ni) with rich S vacancies via a two-step calcination-photo-deposition method. The introduction of rich S vacancies and the formation of Ni Schottky both enhance the absorption of visible light by In2S3 and substantially improve its carrier separation efficiency. Notably, we also found that SvIS/Ni is capable of realizing multi-channel reaction pathways for oxygen reduction and water oxidation to promote the H2O2 generation. Benefiting from the above advantages, the H2O2 yield of SvIS/Ni in the pure water system under visible light irradiation could reach 1146.6 µmol·g−1 h−1, which is 13.4 times that of pure In2S3, and the apparent quantum yield (AQY) at 400 nm can reach 3.58 %. This study provides a novel idea for designing highly efficient photocatalysts by combining defect engineering and heterojunction modification strategies.
{"title":"Construct the sulfur-vacancy rich In2S3/Ni Schottky junction to largely boost the visible light-driven photocatalytic synthesis of hydrogen peroxide","authors":"Xiaolong Tang , Shuxin Zhang , Shuyuan Yu , Yanbin Jiang , Changlin Yu","doi":"10.1016/j.apcata.2025.120658","DOIUrl":"10.1016/j.apcata.2025.120658","url":null,"abstract":"<div><div>The photocatalytic production of H<sub>2</sub>O<sub>2</sub> from H<sub>2</sub>O and O<sub>2</sub> <em>via</em> solar light-driven is a low-cost, safe, and environmentally friendly route for H<sub>2</sub>O<sub>2</sub> production, but the high carrier recombination rate and insufficient active sites in the photocatalytic process greatly limit the efficiency of H<sub>2</sub>O<sub>2</sub> generation. Here, we combined both vacancy modification and heterojunction engineering strategies to modify In<sub>2</sub>S<sub>3</sub>, successfully constructing In<sub>2</sub>S<sub>3</sub>/Ni Schottky junctions (SvIS/Ni) with rich S vacancies <em>via</em> a two-step calcination-photo-deposition method. The introduction of rich S vacancies and the formation of Ni Schottky both enhance the absorption of visible light by In<sub>2</sub>S<sub>3</sub> and substantially improve its carrier separation efficiency. Notably, we also found that SvIS/Ni is capable of realizing multi-channel reaction pathways for oxygen reduction and water oxidation to promote the H<sub>2</sub>O<sub>2</sub> generation. Benefiting from the above advantages, the H<sub>2</sub>O<sub>2</sub> yield of SvIS/Ni in the pure water system under visible light irradiation could reach 1146.6 µmol·g<sup>−1</sup> h<sup>−1</sup>, which is 13.4 times that of pure In<sub>2</sub>S<sub>3</sub>, and the apparent quantum yield (AQY) at 400 nm can reach 3.58 %. This study provides a novel idea for designing highly efficient photocatalysts by combining defect engineering and heterojunction modification strategies.</div></div>","PeriodicalId":243,"journal":{"name":"Applied Catalysis A: General","volume":"709 ","pages":"Article 120658"},"PeriodicalIF":4.8,"publicationDate":"2025-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145413437","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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