Pub Date : 2026-03-01Epub Date: 2026-01-06DOI: 10.1016/j.jcat.2026.116687
Brandon Elliott Oliphant, Zachary W. Meduna, J.Will Medlin
Mixed-aldol condensation of acetaldehyde and acetone was investigated over metal oxide and aluminosilicate catalysts to understand how changing the type of active site affects the selectivity of aldehyde-ketone cross-aldol condensation reactions. On TiO2 and MgO, where basic sites play a central role, high selectivity toward acetaldehyde self-condensation was observed. In contrast, reactions on the aluminosilicates, catalyzed by acid sites, had high selectivity toward the cross-condensation reaction. Temperature programmed desorption (TPD) studies showed that TiO2 binds acetaldehyde and its coupling products strongly, whereas acetone is adsorbed weakly enough to mostly undergo desorption without reaction. Similar studies on amorphous silica-alumina (ASA) showed the existence of both strongly bound acetaldehyde and strongly bound acetone, evidenced by the desorption of acetaldehyde and acetone coupling products. The discrepancy in reactant binding between surfaces is also supported by reaction order studies, which showed that on TiO2 acetone does not displace acetaldehyde from the catalyst surface, whereas on the aluminosilicate catalysts acetone readily displaces acetaldehyde. Kinetic isotope effect experiments showed that although selectivity is different across the two types of catalysts, C–H bond activation to form the nucleophilic enolate is likely kinetically relevant on both materials. High selectivity to cross-condensation was observed on HZSM-5 with a variety of SiO2:Al2O3 ratios, with kinetic results indicating a tradeoff between the number and strength of the active sites.
{"title":"The impact of active site character on the selectivity of aldehyde-ketone cross-aldol condensation reactions","authors":"Brandon Elliott Oliphant, Zachary W. Meduna, J.Will Medlin","doi":"10.1016/j.jcat.2026.116687","DOIUrl":"10.1016/j.jcat.2026.116687","url":null,"abstract":"<div><div>Mixed-aldol condensation of acetaldehyde and acetone was investigated over metal oxide and aluminosilicate catalysts to understand how changing the type of active site affects the selectivity of aldehyde-ketone cross-aldol condensation reactions. On TiO<sub>2</sub> and MgO, where basic sites play a central role, high selectivity toward acetaldehyde self-condensation was observed. In contrast, reactions on the aluminosilicates, catalyzed by acid sites, had high selectivity toward the cross-condensation reaction. Temperature programmed desorption (TPD) studies showed that TiO<sub>2</sub> binds acetaldehyde and its coupling products strongly, whereas acetone is adsorbed weakly enough to mostly undergo desorption without reaction. Similar studies on amorphous silica-alumina (ASA) showed the existence of both strongly bound acetaldehyde and strongly bound acetone, evidenced by the desorption of acetaldehyde and acetone coupling products. The discrepancy in reactant binding between surfaces is also supported by reaction order studies, which showed that on TiO<sub>2</sub> acetone does not displace acetaldehyde from the catalyst surface, whereas on the aluminosilicate catalysts acetone readily displaces acetaldehyde. Kinetic isotope effect experiments showed that although selectivity is different across the two types of catalysts, C–H bond activation to form the nucleophilic enolate is likely kinetically relevant on both materials. High selectivity to cross-condensation was observed on HZSM-5 with a variety of SiO<sub>2</sub>:Al<sub>2</sub>O<sub>3</sub> ratios, with kinetic results indicating a tradeoff between the number and strength of the active sites.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116687"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920474","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-20DOI: 10.1016/j.jcat.2026.116710
Xiao-Rong Wen , Shan-Shan Chen , Wen-Jun Xie , Hong-Ru Li , Liang-Nian He
Electrocatalytic carbon dioxide reduction (eCO2R) to ethylene (C2H4) offers a promising pathway toward carbon–neutral cycles and sustainable chemical synthesis. In eCO2R to C2H4, copper-based electrocatalysts, particularly Cu2O, have been widely used. Nevertheless, product selectivity to C2H4 is still quite limited due to the insufficient enrichment of key intermediates and slow C–C coupling kinetics. Herein, the double-shelled hollow mesoporous Cu2O was fabricated through the soft-templating method. And the cavity size and pore architecture of the resulting Cu2O catalysts could be precisely tailored by adjusting the alkyl chain length of the surfactant templates alkyltrimethylammonium bromides. When applied to eCO2R, the as-prepared Cu2O material with tetradecyltrimethylammonium bromide (TTAB) as template exhibited a remarkable Faradaic efficiency of 43.3 ± 0.8% for C2H4 at an industrial-level current density of 549.8 mA cm−2. Experimental and theoretical investigations reveal that its high activity and selectivity toward C2H4 stem from the suitable cavity configuration, which enriches key *CO intermediates and promotes their dimerization via a spatial confinement effect. This study provides valuable insights into the architectural design of efficient catalysts for CO2-to-C2H4 conversion.
电催化二氧化碳还原（eCO2R）制乙烯（C2H4）为实现碳中性循环和可持续化学合成提供了一条有前途的途径。在eCO2R到C2H4中，铜基电催化剂，特别是Cu2O已被广泛使用。然而，由于关键中间体富集不足和C-C耦合动力学缓慢，产物对C2H4的选择性仍然很有限。本文采用软模板法制备了双壳中空介孔Cu2O。通过调整表面活性剂模板烷基三甲基溴化铵的烷基链长度，可以精确地调整Cu2O催化剂的空腔大小和孔结构。以十四烷基三甲基溴化铵（TTAB）为模板制备的Cu2O材料在工业级电流密度549.8 mA cm−2下，对C2H4的法拉第效率为43.3±0.8%。实验和理论研究表明，其对C2H4的高活性和选择性源于合适的腔体结构，它通过空间约束效应富集了关键的*CO中间体并促进了它们的二聚化。该研究为CO2-to-C2H4转化的高效催化剂的结构设计提供了有价值的见解。
{"title":"Cavity-confined Cu2O nanoreactors for efficient CO2 electroreduction to ethylene","authors":"Xiao-Rong Wen , Shan-Shan Chen , Wen-Jun Xie , Hong-Ru Li , Liang-Nian He","doi":"10.1016/j.jcat.2026.116710","DOIUrl":"10.1016/j.jcat.2026.116710","url":null,"abstract":"<div><div>Electrocatalytic carbon dioxide reduction (eCO<sub>2</sub>R) to ethylene (C<sub>2</sub>H<sub>4</sub>) offers a promising pathway toward carbon–neutral cycles and sustainable chemical synthesis. In eCO<sub>2</sub>R to C<sub>2</sub>H<sub>4</sub>, copper-based electrocatalysts, particularly Cu<sub>2</sub>O, have been widely used. Nevertheless, product selectivity to C<sub>2</sub>H<sub>4</sub> is still quite limited due to the insufficient enrichment of key intermediates and slow C–C coupling kinetics. Herein, the double-shelled hollow mesoporous Cu<sub>2</sub>O was fabricated through the soft-templating method. And the cavity size and pore architecture of the resulting Cu<sub>2</sub>O catalysts could be precisely tailored by adjusting the alkyl chain length of the surfactant templates alkyltrimethylammonium bromides. When applied to eCO<sub>2</sub>R, the as-prepared Cu<sub>2</sub>O material with tetradecyltrimethylammonium bromide (TTAB) as template exhibited a remarkable Faradaic efficiency of 43.3 ± 0.8% for C<sub>2</sub>H<sub>4</sub> at an industrial-level current density of 549.8 mA cm<sup>−2</sup>. Experimental and theoretical investigations reveal that its high activity and selectivity toward C<sub>2</sub>H<sub>4</sub> stem from the suitable cavity configuration, which enriches key *CO intermediates and promotes their dimerization via a spatial confinement effect. This study provides valuable insights into the architectural design of efficient catalysts for CO<sub>2</sub>-to-C<sub>2</sub>H<sub>4</sub> conversion.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116710"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014718","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-21DOI: 10.1016/j.jcat.2026.116706
Jinchuan Zhang , Yunpeng Zou , Shuai Chen , Yang Zhao , Di Jin , Jialin Chen , Jijie Li , Yuewen Mu , Wen-Yan Zan , Fengwei Zhang
Aiming at the critical challenges of competitive hydrogen evolution reaction (HER) and sluggish reaction kinetics in CO2 electroreduction reaction (CO2RR), a uniquely structured nitrogen-doped porous carbon-embedded Ni single-atom catalyst (Ni-N3O2/NPC) was designed and synthesized by virtue of density functional theory (DFT) calculations and mild thermal treatment strategies. The as-synthesized catalyst was verified by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption spectroscopy (XAS) to possess an asymmetric configuration featuring Ni-N3O1 motif with axial oxygen ligand, which agrees well with the DFT modeling. CO2RR results validated that the Ni-N3O2/NPC-400 catalyst exhibited 99% Faraday efficiency for CO (FECO) across a wide potential window of −0.3 to −1.0 V vs. reversible hydrogen electrode (RHE) in flow cell, reaching a maximum FECO of 99.9% at −1.0 V vs. RHE with an turnover frequency (TOF) of 63,579 h−1, showcasing potential for industrial CO2 emission reduction. In situ attenuated total reflection infrared spectroscopy (ATR-IR) further confirmed the formation of key *COOH and *CO intermediates during the CO2RR process. Theoretical calculation unveiled that the axial oxygen ligand in Ni-N3O2 configuration synergistically promoted CO2RR kinetics by inducing electronic polarization. The present work not only provides a theoretical basis for axial ligand engineering to regulate the electronic state of single-atom catalysts, but also opens up a new direction for designing high-efficiency CO2RR catalysts.
{"title":"Axial coordination and asymmetric structure synergistically induce electron polarization at Ni sites to promote efficient CO2 electroreduction into CO","authors":"Jinchuan Zhang , Yunpeng Zou , Shuai Chen , Yang Zhao , Di Jin , Jialin Chen , Jijie Li , Yuewen Mu , Wen-Yan Zan , Fengwei Zhang","doi":"10.1016/j.jcat.2026.116706","DOIUrl":"10.1016/j.jcat.2026.116706","url":null,"abstract":"<div><div>Aiming at the critical challenges of competitive hydrogen evolution reaction (HER) and sluggish reaction kinetics in CO<sub>2</sub> electroreduction reaction (CO<sub>2</sub>RR), a uniquely structured nitrogen-doped porous carbon-embedded Ni single-atom catalyst (Ni-N<sub>3</sub>O<sub>2</sub>/NPC) was designed and synthesized by virtue of density functional theory (DFT) calculations and mild thermal treatment strategies. The as-synthesized catalyst was verified by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption spectroscopy (XAS) to possess an asymmetric configuration featuring Ni-N<sub>3</sub>O<sub>1</sub> motif with axial oxygen ligand, which agrees well with the DFT modeling. CO<sub>2</sub>RR results validated that the Ni-N<sub>3</sub>O<sub>2</sub>/NPC-400 catalyst exhibited 99% Faraday efficiency for CO (FE<sub>CO</sub>) across a wide potential window of −0.3 to −1.0 V <em>vs</em>. reversible hydrogen electrode (RHE) in flow cell, reaching a maximum FE<sub>CO</sub> of 99.9% at −1.0 V <em>vs</em>. RHE with an turnover frequency (TOF) of 63,579 h<sup>−1</sup>, showcasing potential for industrial CO<sub>2</sub> emission reduction. <em>In situ</em> attenuated total reflection infrared spectroscopy (ATR-IR) further confirmed the formation of key *COOH and *CO intermediates during the CO<sub>2</sub>RR process. Theoretical calculation unveiled that the axial oxygen ligand in Ni-N<sub>3</sub>O<sub>2</sub> configuration synergistically promoted CO<sub>2</sub>RR kinetics by inducing electronic polarization. The present work not only provides a theoretical basis for axial ligand engineering to regulate the electronic state of single-atom catalysts, but also opens up a new direction for designing high-efficiency CO<sub>2</sub>RR catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116706"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014717","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-08DOI: 10.1016/j.jcat.2026.116688
Liping Tan, Li Fang, Yao Zhang, Jinglin Tong, Yuxin Zhuang, Chunya Li, Lianqing Chen, Shiwei Jin
Environmentally friendly liquid-phase selective oxidation of alcohols with oxygen as oxidant agent is a green strategy for synthesising nitriles and amides. Therein, the design and preparation of heterogeneous catalysts with high activity and selectivity is a hot research topic in this field. Here, we report that nitrogen-doped manganese oxide catalysts have been synthesized by a hydrothermal method, which can oxidize benzyl alcohol to synthesize benzonitrile and benzamide in a cyanide-free environment with high efficiency. As the reaction time and temperature were 6 h and 150 °C, the conversion of benzyl alcohol (feed dosage: 1 mmol) and the selectivity of benzamide were >99 % and 94 %, respectively. The catalyst could be reused at least 5 times without significantly reducing activity. Additionally, the catalyst exhibits broad applicability, capable of catalyzing the cyanidation of various aromatic and aliphatic alcohols. The enhancement in N-MnO2 catalyst performance is attributed to the introduction of nitrogen, which increases the content of low-valent manganese and oxygen vacancies within the catalyst. It contributes to improved selectivity for benzamide.
{"title":"Nitrogen-doped manganese oxide catalysts boost oxidative cyanation of benzyl alcohols","authors":"Liping Tan, Li Fang, Yao Zhang, Jinglin Tong, Yuxin Zhuang, Chunya Li, Lianqing Chen, Shiwei Jin","doi":"10.1016/j.jcat.2026.116688","DOIUrl":"10.1016/j.jcat.2026.116688","url":null,"abstract":"<div><div>Environmentally friendly liquid-phase selective oxidation of alcohols with oxygen as oxidant agent is a green strategy for synthesising nitriles and amides. Therein, the design and preparation of heterogeneous catalysts with high activity and selectivity is a hot research topic in this field. Here, we report that nitrogen-doped manganese oxide catalysts have been synthesized by a hydrothermal method, which can oxidize benzyl alcohol to synthesize benzonitrile and benzamide in a cyanide-free environment with high efficiency. As the reaction time and temperature were 6 h and 150 °C, the conversion of benzyl alcohol (feed dosage: 1 mmol) and the selectivity of benzamide were >99 % and 94 %, respectively. The catalyst could be reused at least 5 times without significantly reducing activity. Additionally, the catalyst exhibits broad applicability, capable of catalyzing the cyanidation of various aromatic and aliphatic alcohols. The enhancement in N-MnO<sub>2</sub> catalyst performance is attributed to the introduction of nitrogen, which increases the content of low-valent manganese and oxygen vacancies within the catalyst. It contributes to improved selectivity for benzamide.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116688"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920099","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-02DOI: 10.1016/j.jcat.2026.116667
Linzhu Cao , Tianye Gao , Tianyu Qiu , Xin Tao
Precisely tuning the excitonic effect of porous organic semiconductors is essential to achieve efficient photosynthesis of singlet oxygen (1O2) from ground state oxygen (3O2) via energy transfer pathway. In this study, a linkage engineering strategy is proposed to tune the excitonic effect of cyclooctatetrathiophene-based porous organic semiconductor photocatalysts. It is found that altering linear linkers significantly influence the excitonic effect of these semiconductors. Notably, the highly twisted dimethylfluorene-linked COTh-based polymeric system possesses higher exciton binding energy and improved intersystem crossing (ISC) efficiency, which are favorable for photoinduced 1O2 generation through energy transfer pathway. PAF-374 achieved a record-high 1O2 generation rate (133.8 μM min−1) with 98 % selectivity in aerobic photocatalytic system when using furfuryl alcohol as probe. This unique performance enables potential applications for photocatalytic drug synthesis (modafinil and artemisinin) and wastewater treatment over this photocatalyst system. In addition, a detailed structure–property correlation is revealed by theoretical calculations.
{"title":"Optimal photosynthesis of 1O2 via energy transfer over linker-engineered cyclooctatetrathiophene-based porous aromatic frameworks","authors":"Linzhu Cao , Tianye Gao , Tianyu Qiu , Xin Tao","doi":"10.1016/j.jcat.2026.116667","DOIUrl":"10.1016/j.jcat.2026.116667","url":null,"abstract":"<div><div>Precisely tuning the excitonic effect of porous organic semiconductors is essential to achieve efficient photosynthesis of singlet oxygen (<sup>1</sup>O<sub>2</sub>) from ground state oxygen (<sup>3</sup>O<sub>2</sub>) via energy transfer pathway. In this study, a linkage engineering strategy is proposed to tune the excitonic effect of cyclooctatetrathiophene-based porous organic semiconductor photocatalysts. It is found that altering linear linkers significantly influence the excitonic effect of these semiconductors. Notably, the highly twisted dimethylfluorene-linked COTh-based polymeric system possesses higher exciton binding energy and improved intersystem crossing (ISC) efficiency, which are favorable for photoinduced <sup>1</sup>O<sub>2</sub> generation through energy transfer pathway. PAF-374 achieved a record-high <sup>1</sup>O<sub>2</sub> generation rate (133.8 μM min<sup>−1</sup>) with 98 % selectivity in aerobic photocatalytic system when using furfuryl alcohol as probe. This unique performance enables potential applications for photocatalytic drug synthesis (modafinil and artemisinin) and wastewater treatment over this photocatalyst system. In addition, a detailed structure–property correlation is revealed by theoretical calculations.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116667"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895312","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-05DOI: 10.1016/j.jcat.2026.116672
Wanyi Li , Wenbiao Zhang , He Li , Yi Tang , Yahong Zhang
Molybdenum disulfide (MoS2) holds promise in catalysis due to its edge-confined activity, but its structural rigidity and strong in-plane Mo-S bonding limit the exposure of active sites. Herein, we propose a high-curvature support-induced method using ultrasmall ZSM-5 subcrystals (Z-5-SC) to tailor the formation of NiMoS2 on them. The high curvature and abundant external silanol groups of Z-5-SC induce tensile strain and strong interfacial anchoring, generating short and curved NiMoS2 slabs with enhanced sulfur vacancies and Ni-Mo-S phase formation. Compared to nanocrystalline zeolite supports, the NiMoS2/Z-5-SC exhibits 7.3-fold higher hydrodesulfurization (HDS) activity toward 4,6-dimethyldibenzothiophene (kHDS = 0.624 h−1), rapid hydrodenitrogenation (HDN) response with minimized HDS suppression in simultaneous HDS and HDN reactions, and excellent cycling stability over 15 cycles. This work presents an effective curvature-engineering strategy to enhance the catalytic potential of MoS2, offering new insights into the design of engineered two-dimensional materials for hydrotreating and beyond.
{"title":"Zeolite subcrystal-induced formation of short and curved NiMoS2 slabs toward highly efficient hydrodesulfurization","authors":"Wanyi Li , Wenbiao Zhang , He Li , Yi Tang , Yahong Zhang","doi":"10.1016/j.jcat.2026.116672","DOIUrl":"10.1016/j.jcat.2026.116672","url":null,"abstract":"<div><div>Molybdenum disulfide (MoS<sub>2</sub>) holds promise in catalysis due to its edge-confined activity, but its structural rigidity and strong in-plane Mo-S bonding limit the exposure of active sites. Herein, we propose a high-curvature support-induced method using ultrasmall ZSM-5 subcrystals (Z-5-SC) to tailor the formation of NiMoS<sub>2</sub> on them. The high curvature and abundant external silanol groups of Z-5-SC induce tensile strain and strong interfacial anchoring, generating short and curved NiMoS<sub>2</sub> slabs with enhanced sulfur vacancies and Ni-Mo-S phase formation. Compared to nanocrystalline zeolite supports, the NiMoS<sub>2</sub>/Z-5-SC exhibits 7.3-fold higher hydrodesulfurization (HDS) activity toward 4,6-dimethyldibenzothiophene (<em>k<sub>HDS</sub></em> = 0.624 h<sup>−1</sup>), rapid hydrodenitrogenation (HDN) response with minimized HDS suppression in simultaneous HDS and HDN reactions, and excellent cycling stability over 15 cycles. This work presents an effective curvature-engineering strategy to enhance the catalytic potential of MoS<sub>2</sub>, offering new insights into the design of engineered two-dimensional materials for hydrotreating and beyond.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116672"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903496","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-06DOI: 10.1016/j.jcat.2025.116661
Yishuang Wang , Lei Liu , Mingqiang Chen , Defang Liang , Chang Li , Jun Wang , Haosheng Xin
Lignin valorization is crucial for obtaining sustainable fuels and chemicals, however its complex structure challenges efficient conversion. Herein, we designed a Ru-modified Co/attapulgite (CoRux/ATP) catalysts for achieving the catalytic depolymerization of lignin (CDL) under ethanol coupled with H2 medium to liquid fuel and guaiacols. CoRu1/ATP exhibited exceptional catalytic efficiency under optimal conditions, where the yields of liquid product and guaiacols reached 82.82% and 584.67 mg/g, respectively. Experiments with model compounds demonstrated that the addition of Ru could effectively reduce the activation energy of the β-O-4 bond cleavage, which decreased from 78.6 kJ·mol−1 to 73.5 kJ·mol−1. Characterization results indicated that the Ru additive yielded Co–Ru interfaces and its hydrogen spillover effect promoted the reduction of Co3O4 to CoO and metallic Co (Co0) to produce more oxygen vacancies (VO). Additionally, the research on reaction mechanisms revealed VO and CoO phases in CoRu1/ATP enhanced the breakage of C–O bonds of lignin and the adjacent metallic Co and Ru sites and Co–Ru interfaces improved the activation of ethanol and molecular hydrogen into active hydrogen (H*) species to stabilize reactive intermediates and enhance hydrogenation reaction. The findings provide a potential method for directional lignin conversion.
{"title":"Efficient depolymerization of lignin over Ru-modified Co/attapulgite: Construct of abundant activated hydrogen source sites","authors":"Yishuang Wang , Lei Liu , Mingqiang Chen , Defang Liang , Chang Li , Jun Wang , Haosheng Xin","doi":"10.1016/j.jcat.2025.116661","DOIUrl":"10.1016/j.jcat.2025.116661","url":null,"abstract":"<div><div>Lignin valorization is crucial for obtaining sustainable fuels and chemicals, however its complex structure challenges efficient conversion. Herein, we designed a Ru-modified Co/attapulgite (CoRu<sub>x</sub>/ATP) catalysts for achieving the catalytic depolymerization of lignin (CDL) under ethanol coupled with H<sub>2</sub> medium to liquid fuel and guaiacols. CoRu<sub>1</sub>/ATP exhibited exceptional catalytic efficiency under optimal conditions, where the yields of liquid product and guaiacols reached 82.82% and 584.67 mg/g, respectively. Experiments with model compounds demonstrated that the addition of Ru could effectively reduce the activation energy of the β-O-4 bond cleavage, which decreased from 78.6 kJ·mol<sup>−1</sup> to 73.5 kJ·mol<sup>−1</sup>. Characterization results indicated that the Ru additive yielded Co–Ru interfaces and its hydrogen spillover effect promoted the reduction of Co<sub>3</sub>O<sub>4</sub> to CoO and metallic Co (Co<sup>0</sup>) to produce more oxygen vacancies (V<sub>O</sub>). Additionally, the research on reaction mechanisms revealed V<sub>O</sub> and CoO phases in CoRu<sub>1</sub>/ATP enhanced the breakage of C–O bonds of lignin and the adjacent metallic Co and Ru sites and Co–Ru interfaces improved the activation of ethanol and molecular hydrogen into active hydrogen (H*) species to stabilize reactive intermediates and enhance hydrogenation reaction. The findings provide a potential method for directional lignin conversion.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116661"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908156","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-21DOI: 10.1016/j.jcat.2026.116705
Martin Hedevang , Lars Mohrhusen , Filip Hallböök , Dorotea Gajdek , Lindsay R. Merte , Sara Blomberg , Jeppe V. Lauritsen
Hydrodeoxygenation (HDO) is a catalytic process applied for the reduction of oxygen levels in hydrocarbons from bio-derived feedstock as part of the processing into renewable fuel. The MoS2-based hydrotreating catalysts, currently being applied for the HDO reaction, are exposed to a complex environment consisting of O-rich hydrocarbons and water, which adversely impacts the state and stability of the catalyst. Here, we analyze the structural and chemical state changes of MoS2 in HDO-relevant conditions using a combination of surface-sensitive techniques applied to a planar model system consisting of supported and structurally well-defined single-layer MoS2 nanoparticles supported on Au(111). As observed by scanning tunnelling microscopy and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), the exposure to mbar pressure of H2O at 600 K induces clear changes in both the shape and size of the MoS2 nanoparticles, explained by a preferential oxidation and etching of MoS2 edges. MoOx is observed on the surface due to the spatial separation of the oxide and etched sulfide phase. Interestingly, when H2/H2O gas mixtures are applied, the sulfur reduction and oxidation of MoS2 appear to be decoupled, indicating that the removal of edge S species is not a prerequisite for oxidation. Furthermore, the formed MoOx showed a preferred reduction of the oxide over the sulfide. Importantly, the atom-resolved imaging reveals that the progressive etching and phase segregation of MoS2 maintains access to pristine edge sites of the single-layer MoS2, explaining why HDO activity can be maintained even for highly oxidized catalysts.
{"title":"In-situ NAP-XPS reveals water-induced phase segregation of MoS2 nanoparticles in hydrodeoxygenation catalysis","authors":"Martin Hedevang , Lars Mohrhusen , Filip Hallböök , Dorotea Gajdek , Lindsay R. Merte , Sara Blomberg , Jeppe V. Lauritsen","doi":"10.1016/j.jcat.2026.116705","DOIUrl":"10.1016/j.jcat.2026.116705","url":null,"abstract":"<div><div>Hydrodeoxygenation (HDO) is a catalytic process applied for the reduction of oxygen levels in hydrocarbons from bio-derived feedstock as part of the processing into renewable fuel. The MoS<sub>2</sub>-based hydrotreating catalysts, currently being applied for the HDO reaction, are exposed to a complex environment consisting of O-rich hydrocarbons and water, which adversely impacts the state and stability of the catalyst. Here, we analyze the structural and chemical state changes of MoS<sub>2</sub> in HDO-relevant conditions using a combination of surface-sensitive techniques applied to a planar model system consisting of supported and structurally well-defined single-layer MoS<sub>2</sub> nanoparticles supported on Au(111). As observed by scanning tunnelling microscopy and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS), the exposure to mbar pressure of H<sub>2</sub>O at 600 K induces clear changes in both the shape and size of the MoS<sub>2</sub> nanoparticles, explained by a preferential oxidation and etching of MoS<sub>2</sub> edges. MoO<sub>x</sub> is observed on the surface due to the spatial separation of the oxide and etched sulfide phase. Interestingly, when H<sub>2</sub>/H<sub>2</sub>O gas mixtures are applied, the sulfur reduction and oxidation of MoS<sub>2</sub> appear to be decoupled, indicating that the removal of edge S species is not a prerequisite for oxidation. Furthermore, the formed MoO<sub>x</sub> showed a preferred reduction of the oxide over the sulfide. Importantly, the atom-resolved imaging reveals that the progressive etching and phase segregation of MoS<sub>2</sub> maintains access to pristine edge sites of the single-layer MoS<sub>2</sub>, explaining why HDO activity can be maintained even for highly oxidized catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116705"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146005830","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-20DOI: 10.1016/j.jcat.2026.116708
Xiaoqian Bai , Jialong Lin , Bingxue Cheng , Chunqi Yang , Xinlin Wang , Yuhang Li , Tamao Ishida , Toru Murayama , Guangli Xiu , Mingyue Lin
Ethylene glycol (EG), a primary byproduct from the alkaline hydrolysis of polyethylene terephthalate (PET), can serve as an alternative anode reaction to the oxygen evolution reaction (OER). This substitution significantly lowers the energy required for hydrogen production via water electrolysis. In this study, Fe(0.3 wt%)-CoPO was in situ synthesized on nickel foam (NF), showing great electrocatalytic activity. At just 1.426 V (vs. RHE), it achieves a current density of 100 mA cm−2 and a Faraday efficiency (FE) of 100%. At the 100 mA cm−2, the potential of the ethylene glycol oxidation reaction (EGOR) was 224 mV lower than that of OER, thereby reducing the total working potential and consequently lowering the energy consumption for hydrogen production at the cathode. In situ Raman spectroscopy further reveals that the high activity of EGOR is due to the generation of CoOOH species during the electrochemical reconstruction. Additionally, Fe incorporation has the effect of inhibiting the overoxidation of Co3+. This study successfully couples EGOR electrocatalysis with the production of valuable chemicals and hydrogen, providing new insights into high-performance EGOR catalytic systems.
乙二醇（EG）是聚对苯二甲酸乙二醇酯（PET）碱性水解的主要副产物，可以作为析氧反应（OER）的备选阳极反应。这种替代显著降低了通过水电解制氢所需的能量。本研究在泡沫镍（NF）上原位合成了Fe(0.3 wt%)-CoPO，表现出良好的电催化活性。在1.426 V （vs. RHE）下，它实现了100 mA cm−2的电流密度和100%的法拉第效率（FE）。在100 mA cm−2下，乙二醇氧化反应（EGOR）的电位比OER的电位低224 mV，从而降低了总工作电位，从而降低了阴极制氢的能耗。原位拉曼光谱进一步揭示了EGOR的高活性是由于电化学重构过程中CoOOH物质的生成。此外，铁的掺入还具有抑制Co3+过氧化的作用。该研究成功地将EGOR电催化与有价化学品和氢气的生产结合起来，为高性能EGOR催化系统提供了新的见解。
{"title":"Fe-induced Co (IV) elimination enhancing selective ethylene glycol oxidation at high current density","authors":"Xiaoqian Bai , Jialong Lin , Bingxue Cheng , Chunqi Yang , Xinlin Wang , Yuhang Li , Tamao Ishida , Toru Murayama , Guangli Xiu , Mingyue Lin","doi":"10.1016/j.jcat.2026.116708","DOIUrl":"10.1016/j.jcat.2026.116708","url":null,"abstract":"<div><div>Ethylene glycol (EG), a primary byproduct from the alkaline hydrolysis of polyethylene terephthalate (PET), can serve as an alternative anode reaction to the oxygen evolution reaction (OER). This substitution significantly lowers the energy required for hydrogen production via water electrolysis. In this study, Fe(0.3 wt%)-CoPO was <em>in situ</em> synthesized on nickel foam (NF), showing great electrocatalytic activity. At just 1.426 V (<em>vs.</em> RHE), it achieves a current density of 100 mA cm<sup>−2</sup> and a Faraday efficiency (FE) of 100%. At the 100 mA cm<sup>−2</sup>, the potential of the ethylene glycol oxidation reaction (EGOR) was 224 mV lower than that of OER, thereby reducing the total working potential and consequently lowering the energy consumption for hydrogen production at the cathode. <em>In situ</em> Raman spectroscopy further reveals that the high activity of EGOR is due to the generation of CoOOH species during the electrochemical reconstruction. Additionally, Fe incorporation has the effect of inhibiting the overoxidation of Co<sup>3+</sup>. This study successfully couples EGOR electrocatalysis with the production of valuable chemicals and hydrogen, providing new insights into high-performance EGOR catalytic systems.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116708"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146014715","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-06DOI: 10.1016/j.jcat.2026.116673
Jorge Ferreira Jr. , Gabriela Uez , Arthur L. Schmidt , Camila Ebersol , Bianca T. Dalberto , Daniel F. Pietezak , Robson S. Oliboni , Angélica V. Moro , Diogo S. Lüdtke , Adriana C.A. Casagrande , Fabiano S. Rodembusch , Pedro Migowski , Osvaldo L. Casagrande Jr.
We report the design, synthesis, and comprehensive characterization of a new series of iron(II) complexes bearing bis(pyrazolyl)phenantroline ligands, developed as homogeneous catalysts for the visible-light-driven reduction of CO2 to CO. All complexes adopt high-spin quintet ground states and exhibit distorted octahedral geometries, with redox processes primarily localized on the ligand framework. Spectroscopic data and theoretical modeling revealed that the optical absorption in the UV region arises from ligand-centered π–π* transitions, while the weaker red-shifted bands are attributed to forbidden transitions. Electrochemical analyses confirmed ligand-centered reductions across the series, modulated by the electronic nature of the pyrazolyl substituents. All iron complexes were active for photocatalytic reduction of CO2 to CO. Among them, Fe2 showed the highest overall activity, reaching a TONCO of 1318 and CO selectivity of 84 %. Notably, Fe4 achieved a high TONCO of 1265 and CO selectivity of 91 % in the series. Systematic variation of reaction parameters using Fe2 allowed the identification of optimal conditions for maximizing catalytic efficiency and product selectivity. At lower catalyst loadings, Fe2 achieved the highest TONCO (up to 23,138) and CO selectivity (up to 91 %). Additionally, the presence of 7.5–10 % water proved essential for effective proton-coupled electron transfer and stabilization of intermediates. Mechanistic studies, including control and Hg poisoning experiments, confirmed the homogeneous nature and robustness of the catalytic system, with deactivation arising mainly from photosensitizer deterioration. Fe2 reached a TONCO of 9754 after 4 h of irradiation (λ = 462 nm), corresponding to a TOF of 2438 h−1 and a total quantum yield of 8.24 %.
{"title":"Iron(II) bis(pyrazolyl)phenanthroline complexes as robust and efficient homogeneous catalysts for CO2-to-CO conversion under visible light","authors":"Jorge Ferreira Jr. , Gabriela Uez , Arthur L. Schmidt , Camila Ebersol , Bianca T. Dalberto , Daniel F. Pietezak , Robson S. Oliboni , Angélica V. Moro , Diogo S. Lüdtke , Adriana C.A. Casagrande , Fabiano S. Rodembusch , Pedro Migowski , Osvaldo L. Casagrande Jr.","doi":"10.1016/j.jcat.2026.116673","DOIUrl":"10.1016/j.jcat.2026.116673","url":null,"abstract":"<div><div>We report the design, synthesis, and comprehensive characterization of a new series of iron(II) complexes bearing bis(pyrazolyl)phenantroline ligands, developed as homogeneous catalysts for the visible-light-driven reduction of CO<sub>2</sub> to CO. All complexes adopt high-spin quintet ground states and exhibit distorted octahedral geometries, with redox processes primarily localized on the ligand framework. Spectroscopic data and theoretical modeling revealed that the optical absorption in the UV region arises from ligand-centered π–π* transitions, while the weaker red-shifted bands are attributed to forbidden transitions. Electrochemical analyses confirmed ligand-centered reductions across the series, modulated by the electronic nature of the pyrazolyl substituents. All iron complexes were active for photocatalytic reduction of CO<sub>2</sub> to CO. Among them, <strong>Fe2</strong> showed the highest overall activity, reaching a TON<sub>CO</sub> of 1318 and CO selectivity of 84 %. Notably, <strong>Fe4</strong> achieved a high TON<sub>CO</sub> of 1265 and CO selectivity of 91 % in the series. Systematic variation of reaction parameters using <strong>Fe2</strong> allowed the identification of optimal conditions for maximizing catalytic efficiency and product selectivity. At lower catalyst loadings, <strong>Fe2</strong> achieved the highest TON<sub>CO</sub> (up to 23,138) and CO selectivity (up to 91 %). Additionally, the presence of 7.5–10 % water proved essential for effective proton-coupled electron transfer and stabilization of intermediates. Mechanistic studies, including control and Hg poisoning experiments, confirmed the homogeneous nature and robustness of the catalytic system, with deactivation arising mainly from photosensitizer deterioration. <strong>Fe2</strong> reached a TON<sub>CO</sub> of 9754 after 4 h of irradiation (λ = 462 nm), corresponding to a TOF of 2438 h<sup>−1</sup> and a total quantum yield of 8.24 %.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116673"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145908190","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"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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