Pub 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":"2026-01-02","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 : 2025-12-31DOI: 10.1016/j.jcat.2025.116663
Ye Xu , Timm McNeese
Sulfonamides are a group of synthetic compounds widely used in human and veterinarian medicine (a.k.a. sulfa drugs) and can accumulate in the environment. We show theoretically that ceria can catalyze the hydrolysis of sulfonamides via S − N bond scission over a pair of Ce-O lattice sites, where Olatt attacks the S center and displaces the N center in a nucleophilic substitution, yielding a primary amine and a sulfonic acid as products. Our calculations shed light on how different substituents on the S and N centers affect S − N bond scission by comparing non-aromatic vs. aromatic groups, homo- vs. heterocyclic aromaticity, and further functionalization of the aromatic groups. Stabilizing the S and N centers is found to have the opposite effects on the facility of S -− N bond scission. The desorption of sulfonic acid is strongly endothermic in the gas phase but is calculated to be facilitated by solvation effects when sulfonic acid undergoes acid-base titration with the amine product to form an oxyanion and a pyridinium cation, or when it self-ionizes to a zwitterion.
{"title":"Theoretical investigation of decomposition and hydrolysis of sulfonamides on CeO2(111)","authors":"Ye Xu , Timm McNeese","doi":"10.1016/j.jcat.2025.116663","DOIUrl":"10.1016/j.jcat.2025.116663","url":null,"abstract":"<div><div>Sulfonamides are a group of synthetic compounds widely used in human and veterinarian medicine (a.k.a. sulfa drugs) and can accumulate in the environment. We show theoretically that ceria can catalyze the hydrolysis of sulfonamides via S − N bond scission over a pair of Ce-O lattice sites, where O<sub>latt</sub> attacks the S center and displaces the N center in a nucleophilic substitution, yielding a primary amine and a sulfonic acid as products. Our calculations shed light on how different substituents on the S and N centers affect S − N bond scission by comparing non-aromatic vs. aromatic groups, homo- vs. heterocyclic aromaticity, and further functionalization of the aromatic groups. Stabilizing the S and N centers is found to have the opposite effects on the facility of S -− N bond scission. The desorption of sulfonic acid is strongly endothermic in the gas phase but is calculated to be facilitated by solvation effects when sulfonic acid undergoes acid-base titration with the amine product to form an oxyanion and a pyridinium cation, or when it self-ionizes to a zwitterion.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116663"},"PeriodicalIF":6.5,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895324","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 : 2025-12-31DOI: 10.1016/j.jcat.2025.116665
Yongqi Kuang , Jiawen Ma , Sibudjing Kawi , Shuzhuang Sun , Yuqianer Zeng , Lina Liu
CO2 reforming of tar reaction (CRT) is a promising method for simultaneous removal and conversion of CO2 and tar in syngas from the biomass gasification technology, which is essential for utilization and upgrading of syngas. However, the deactivation of supported Ni catalysts by sintering and carbon deposits remains the most challenging issue. In this study, (Mg, Al, Ce)Ox nanosheet-supported Ni-based catalysts with varying Ce/Ni ratios (0, 0.1, 0.2, 0.3) were constructed from freeze-dried Ni–Ce–Mg–Al LDH precursors with the thermally dried Ni–Ce0.2–Mg–Al LDH as a reference. The result suggested that freeze drying favored the achievement of loose nanosheets and highly dispersed metals. With the optimized Ce dosage (Ce/Ni = 0.2), the Ni–Ce0.2–F–R catalyst exhibited the most superior activity and stability over 40h time-on-stream. The possible reason is that Ni–Ce0.2–F–R catalyst possessed abundant and homogeneously distributed Ni–CeO2 interface, which accelerated the electron transfer from CeO2 to Ni via Ni–Ov–Ce structure (Ov, oxygen vacancy). An electron-rich state of Ni was thus achieved, which could effectively activate the C–H and C–C bonds. Furthermore, the abundant oxygen defects and stronger alkaline sites of the CeO2 support promoted the adsorption and activation of CO2, which was conducive to the elimination of coke adjacent Ni metal sites. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) suggested that the abundant surface-active oxygen species facilitated the deep oxidation and ring opening of the benzene ring.
CO2重整焦油反应（CRT）是生物质气化技术中合成气中CO2和焦油同时脱除和转化的一种有前景的方法，对合成气的利用和升级至关重要。然而，通过烧结和积碳使负载型镍催化剂失活仍然是最具挑战性的问题。在本研究中，以Ni- ce0.2 - Mg - Al LDH为参考，以冷冻干燥的Ni- Ce - Ce - Al LDH为前驱体，构建了不同Ce/Ni比率（0、0.1、0.2、0.3）的（Mg, Al, Ce）Ox纳米片负载的Ni基催化剂。结果表明，冷冻干燥有利于获得松散的纳米片和高度分散的金属。当Ce/Ni = 0.2时，Ni - ce0.2 - f - r催化剂在40h的反应时间内表现出最优的活性和稳定性。可能的原因是Ni - ce0.2 - f - r催化剂具有丰富且分布均匀的Ni - CeO2界面，通过Ni - Ov - ce结构（Ov，氧空位）加速了电子从CeO2向Ni的转移。镍的富电子态可以有效地激活C-H和C-C键。此外，CeO2载体丰富的氧缺陷和较强的碱性位点促进了CO2的吸附和活化，有利于消除邻近Ni金属位点的焦炭。原位漫反射红外傅里叶变换光谱（DRIFTS）表明，丰富的表面活性氧促进了苯环的深度氧化和开环。
{"title":"Enhanced charge transfer and oxygen vacancies by interface engineering for CO2 reforming of toluene","authors":"Yongqi Kuang , Jiawen Ma , Sibudjing Kawi , Shuzhuang Sun , Yuqianer Zeng , Lina Liu","doi":"10.1016/j.jcat.2025.116665","DOIUrl":"10.1016/j.jcat.2025.116665","url":null,"abstract":"<div><div>CO<sub>2</sub> reforming of tar reaction (CRT) is a promising method for simultaneous removal and conversion of CO<sub>2</sub> and tar in syngas from the biomass gasification technology, which is essential for utilization and upgrading of syngas. However, the deactivation of supported Ni catalysts by sintering and carbon deposits remains the most challenging issue. In this study, (Mg, Al, Ce)O<sub>x</sub> <!-->nanosheet-supported Ni-based catalysts with varying Ce/Ni ratios (0, 0.1, 0.2, 0.3) were constructed from freeze-dried Ni–Ce–Mg–Al LDH precursors with the thermally dried Ni–Ce<sub>0.2</sub>–Mg–Al LDH as a reference. The result suggested that freeze drying favored the achievement of loose nanosheets and highly dispersed metals. With the optimized Ce dosage (Ce/Ni = 0.2), the Ni–Ce<sub>0.2</sub>–F–R catalyst exhibited the most superior activity and stability over 40h time-on-stream. The possible reason is that Ni–Ce<sub>0.2</sub>–F–R catalyst possessed abundant and homogeneously distributed<!--> <!-->Ni–CeO<sub>2</sub> interface, which accelerated the electron transfer from CeO<sub>2</sub> to Ni via Ni–O<sub>v</sub>–Ce structure (Ov, oxygen vacancy). An electron-rich state of Ni was thus achieved, which could effectively activate the C–H and C–C bonds. Furthermore, the abundant oxygen defects and stronger alkaline sites of the CeO<sub>2</sub> support promoted the adsorption and activation of CO<sub>2</sub>, which was conducive to the elimination of coke adjacent Ni metal sites. <em>In situ</em> diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) suggested that the abundant surface-active oxygen species facilitated the deep oxidation and ring opening of the benzene ring.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116665"},"PeriodicalIF":6.5,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895321","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 : 2025-12-31DOI: 10.1016/j.jcat.2025.116664
Jiali Wang , Jiajun Lu , Xiuwen Zhao , Guichao Hu , Xiaobo Yuan , Junfeng Ren , Siyun Qi
Dynamic control of catalytic activity remains a major challenge for conventional single-atom catalysts (SACs) whose coordination environments are fixed after construction. In this work, CuInP2S6 (CIPS) was employed as a model ferroelectric support to explore how polarization switching modulates catalytic behavior in transition metal single atoms (TM@CIPS) for hydrogen and oxygen evolution reactions (HER and OER). Fifteen transition metals across the 3d-5d series were examined under two polarization states to evaluate the stability and catalytic properties. Polarization switching between upward and downward states was found to dynamically tune catalytic activity, markedly reducing OER overpotentials in systems such as Co@CIPS and Pt@CIPS by optimizing reaction pathways. This enhancement originated from polarization-induced redistribution of interfacial charge, which shifted the d-band center and modified TM-O bonding strength, thereby governing adsorption and reaction energetics. These results establish ferroelectric polarization as an effective strategy for real-time control of catalytic processes and provide fundamental insight for designing next-generation catalysts.
{"title":"Ferroelectric polarization switching regulates single-atom catalysis for water splitting","authors":"Jiali Wang , Jiajun Lu , Xiuwen Zhao , Guichao Hu , Xiaobo Yuan , Junfeng Ren , Siyun Qi","doi":"10.1016/j.jcat.2025.116664","DOIUrl":"10.1016/j.jcat.2025.116664","url":null,"abstract":"<div><div>Dynamic control of catalytic activity remains a major challenge for conventional single-atom catalysts (SACs) whose coordination environments are fixed after construction. In this work, CuInP<sub>2</sub>S<sub>6</sub> (CIPS) was employed as a model ferroelectric support to explore how polarization switching modulates catalytic behavior in transition metal single atoms (TM@CIPS) for hydrogen and oxygen evolution reactions (HER and OER). Fifteen transition metals across the <em>3d</em>-<em>5d</em> series were examined under two polarization states to evaluate the stability and catalytic properties. Polarization switching between upward and downward states was found to dynamically tune catalytic activity, markedly reducing OER overpotentials in systems such as Co@CIPS and Pt@CIPS by optimizing reaction pathways. This enhancement originated from polarization-induced redistribution of interfacial charge, which shifted the <em>d</em>-band center and modified TM-O bonding strength, thereby governing adsorption and reaction energetics. These results establish ferroelectric polarization as an effective strategy for real-time control of catalytic processes and provide fundamental insight for designing next-generation catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116664"},"PeriodicalIF":6.5,"publicationDate":"2025-12-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880461","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 : 2025-12-30DOI: 10.1016/j.jcat.2025.116662
Dan Wang , Youxi Wang , Qingqing Wang , Xiaolin Tan , Zhe Li , Xuefeng Cui , Shijing Tan , Zhenyu Li , Bing Wang , Xiang Shao
Semiconductor oxide-based heterogeneous catalysis and/or photocatalysis provide pivotal solutions to global energy and environmental crises, yet a fundamental understanding of their atomic-level mechanisms lags far behind the practical applications. A typical example is the degradation of formaldehyde (FA) on ZnO surfaces. Although ZnO is extensively employed in sensing and removing FA from the atmosphere, the atomic-level reaction mechanisms remain unclear. Here, we combine scanning tunneling microscopy (STM), temperature-programmed desorption (TPD) measurements, and density functional theory (DFT) calculations to reveal the reaction process of FA on a ZnO() single-crystalline surface. We directly visualize two competing pathways: dissociation versus dimerization, with dimerization getting significantly accelerated upon ultraviolet (UV) irradiation at room temperature (RT). Furthermore, at elevated temperatures, intermediates react aggressively with surface lattice oxygen, generating abundant oxygen vacancies–a discovery that fundamentally advances our understanding of the Mars-van Krevelen mechanism for FA and similar organics on ZnO. These atomic-level insights open new avenues for designing highly efficient, environment friendly photocatalytic systems based on the semiconducting oxide materials.
{"title":"Atomistic visualization of formaldehyde degradation on the ZnO surface through a Mars-van Krevelen mechanism","authors":"Dan Wang , Youxi Wang , Qingqing Wang , Xiaolin Tan , Zhe Li , Xuefeng Cui , Shijing Tan , Zhenyu Li , Bing Wang , Xiang Shao","doi":"10.1016/j.jcat.2025.116662","DOIUrl":"10.1016/j.jcat.2025.116662","url":null,"abstract":"<div><div>Semiconductor oxide-based heterogeneous catalysis and/or photocatalysis provide pivotal solutions to global energy and environmental crises, yet a fundamental understanding of their atomic-level mechanisms lags far behind the practical applications. A typical example is the degradation of formaldehyde (FA) on ZnO surfaces. Although ZnO is extensively employed in sensing and removing FA from the atmosphere, the atomic-level reaction mechanisms remain unclear. Here, we combine scanning tunneling microscopy (STM), temperature-programmed desorption (TPD) measurements, and density functional theory (DFT) calculations to reveal the reaction process of FA on a ZnO(<span><math><mrow><mn>10</mn><mover><mrow><mn>1</mn></mrow><mrow><mo>¯</mo></mrow></mover><mn>0</mn></mrow></math></span>) single-crystalline surface. We directly visualize two competing pathways: dissociation versus dimerization, with dimerization getting significantly accelerated upon ultraviolet (UV) irradiation at room temperature (RT). Furthermore, at elevated temperatures, intermediates react aggressively with surface lattice oxygen, generating abundant oxygen vacancies–a discovery that fundamentally advances our understanding of the Mars-van Krevelen mechanism for FA and similar organics on ZnO. These atomic-level insights open new avenues for designing highly efficient, environment friendly photocatalytic systems based on the semiconducting oxide materials.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116662"},"PeriodicalIF":6.5,"publicationDate":"2025-12-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145880367","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 : 2025-12-27DOI: 10.1016/j.jcat.2025.116657
Hao-Xue Bi , Hui-Hui Ru , Jing Du, Yuan-Yuan Ma, Lan-Zhi Wang, Zhan-Gang Han
One-pot domino synthesis of benzodiazepines represents an efficient, environmentally benign, and atom-economical pathway; however, it necessitates the development of multifunctional and highly efficient acid catalysts. Herein, employing a stepwise assembly strategy, a series of novel lanthanide metal ions-incorporated fully reduced phosphomolybdate frameworks with the general formula [M(H2O)5][M(H2O)3]2[M(H2O)4]4[Mn(P4Mo6O31H6)2][MnH11(P4Mo6O31)2]·nH2O (M = Tb3+, n = 38 in 1; Dy3+, n = 41 in 2; Ho3+, n = 39 in 3; Er3+, n = 40 in 4), were synthesized as dual-acid catalysts for the one-pot, three-component domino construction of 1,5-benzodiazepines. In crystals 1–4, mono- and dinuclear lanthanide cations with Lewis acidity bridge Mn{P4Mo6}2 clusters exhibiting Brǿnsted-acid activity, generating three-dimensional, all-inorganic isostructural frameworks that constitute a tunable acid-catalysis platform. In the one-pot, three-component domino reaction of 1,5-benzodiazepines synthesis, crystal 1 (Tb-Mn{P4Mo6}2) achieved the 88 % yield of 1,5-benzodiazepine product within 12 h, which is superior to that of crystal 2 (Dy-Mn{P4Mo6}2, 83 %), crystal 3 (Ho-Mn{P4Mo6}2, 76 %) and crystal 4 (Er-Mn{P4Mo6}2, 73 %). Mechanistic studies revealed that Ln3+ and {Mn[P4Mo6O31]2}22− (Mn{P4Mo6}2) as dual Lewis-Brǿnsted acid sites play significant roles for activating organic carbonyl and enamine bonds to form the seven-membered diazaheterocyclic ring of benzodiazepine products by condensation and addition reactions. The different lanthanide metal ions regulated the Lewis acid activities of catalysts. This work provides a molecular level compositional control strategy for the design and preparation of efficient polyoxometalate-based multifunctional acid catalysts.
{"title":"Tailoring dual-acid sites in lanthanide-incorporated fully reduced phosphomolybdates for the synthesis of polycyclic fused benzodiazepines","authors":"Hao-Xue Bi , Hui-Hui Ru , Jing Du, Yuan-Yuan Ma, Lan-Zhi Wang, Zhan-Gang Han","doi":"10.1016/j.jcat.2025.116657","DOIUrl":"10.1016/j.jcat.2025.116657","url":null,"abstract":"<div><div>One-pot domino synthesis of benzodiazepines represents an efficient, environmentally benign, and atom-economical pathway; however, it necessitates the development of multifunctional and highly efficient acid catalysts. Herein, employing a stepwise assembly strategy, a series of novel lanthanide metal ions-incorporated fully reduced phosphomolybdate frameworks with the general formula [M(H<sub>2</sub>O)<sub>5</sub>][M(H<sub>2</sub>O)<sub>3</sub>]<sub>2</sub>[M(H<sub>2</sub>O)<sub>4</sub>]<sub>4</sub>[Mn(P<sub>4</sub>Mo<sub>6</sub>O<sub>31</sub>H<sub>6</sub>)<sub>2</sub>][MnH<sub>11</sub>(P<sub>4</sub>Mo<sub>6</sub>O<sub>31</sub>)<sub>2</sub>]·nH<sub>2</sub>O (M = Tb<sup>3+</sup>, n = 38 in <strong>1</strong>; Dy<sup>3+</sup>, n = 41 in <strong>2</strong>; Ho<sup>3+</sup>, n = 39 in <strong>3</strong>; Er<sup>3+</sup>, n = 40 in <strong>4</strong>), were synthesized as dual-acid catalysts for the one-pot, three-component domino construction of 1,5-benzodiazepines. In crystals <strong>1</strong>–<strong>4</strong>, mono- and dinuclear lanthanide cations with Lewis acidity bridge Mn{P<sub>4</sub>Mo<sub>6</sub>}<sub>2</sub> clusters exhibiting Brǿnsted-acid activity, generating three-dimensional, all-inorganic isostructural frameworks that constitute a tunable acid-catalysis platform. In the one-pot, three-component domino reaction of 1,5-benzodiazepines synthesis, crystal <strong>1</strong> (Tb-Mn{P<sub>4</sub>Mo<sub>6</sub>}<sub>2</sub>) achieved the 88 % yield of 1,5-benzodiazepine product within 12 h, which is superior to that of crystal <strong>2</strong> (Dy-Mn{P<sub>4</sub>Mo<sub>6</sub>}<sub>2</sub>, 83 %), crystal <strong>3</strong> (Ho-Mn{P<sub>4</sub>Mo<sub>6</sub>}<sub>2</sub>, 76 %) and crystal <strong>4</strong> (Er-Mn{P<sub>4</sub>Mo<sub>6</sub>}<sub>2</sub>, 73 %). Mechanistic studies revealed that Ln<sup>3+</sup> and {Mn[P<sub>4</sub>Mo<sub>6</sub>O<sub>31</sub>]<sub>2</sub>}<sup>22−</sup> (Mn{P<sub>4</sub>Mo<sub>6</sub>}<sub>2</sub>) as dual Lewis-Brǿnsted acid sites play significant roles for activating organic carbonyl and enamine bonds to form the seven-membered diazaheterocyclic ring of benzodiazepine products by condensation and addition reactions. The different lanthanide metal ions regulated the Lewis acid activities of catalysts. This work provides a molecular level compositional control strategy for the design and preparation of efficient polyoxometalate-based multifunctional acid catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116657"},"PeriodicalIF":6.5,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145845449","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 : 2025-12-27DOI: 10.1016/j.jcat.2025.116646
Yicong Yan , Jin Yuan , Hongbo Zhang
Highly dispersed cobalt catalyst attracts great attention in two-electron oxygen reduction reaction (2e− ORR) toward hydrogen peroxide (H2O2) due to their superior reactivities, however, it generally suffers from low selectivity and limited understandings on the reaction mechanism. Here, Co2@C3N4 nanocomposite has been primarily established through the pyrolysis of dimeric cobalt complex, which mainly constitutes dual-atoms of Co and exhibited exceptional H2O2 production performance, achieving a Faradaic efficiency (FE) of ∼ 90% at −0.4 V vs. RHE and a production rate of 2.38 mol L−1 gcat−1 h−1, surpassing most reported SACs in H-cell systems. This enhancement is attributed to the dual site structure of Co and defect-rich interfaces constructed, which promote the O-O bond stabilization and optimize the reactivity/selectivity of H2O2 generation, which was found to be controlled by **OOH generation through an electron coupled proton transfer elementary steps over a proton covered surface.
高分散钴催化剂因其优异的反应活性在过氧化氢（H2O2）的双电子氧还原反应（2e - ORR）中备受关注，但其选择性低，对反应机理的认识有限。在这里，Co2@C3N4纳米复合材料主要是通过二聚体钴配合物的热解建立的，该配合物主要由Co的双原子组成，具有优异的H2O2生成性能，在- 0.4 V vs. RHE下，法拉第效率（FE）为 ~ 90 %，产率为2.38 mol L−1 gcat−1h−1，超过了h电池系统中大多数报道的SACs。这种增强归因于Co和富缺陷界面的双位结构，促进了O-O键的稳定，优化了H2O2生成的反应性/选择性，发现这是由**OOH生成控制的，通过电子耦合质子转移基本步骤在质子覆盖的表面上进行。
{"title":"Constructing Co2@C3N4 dual-atomic site for highly efficient electrochemical H2O2 production","authors":"Yicong Yan , Jin Yuan , Hongbo Zhang","doi":"10.1016/j.jcat.2025.116646","DOIUrl":"10.1016/j.jcat.2025.116646","url":null,"abstract":"<div><div>Highly dispersed cobalt catalyst attracts great attention in two-electron oxygen reduction reaction (2e<sup>−</sup> ORR) toward hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) due to their superior reactivities, however, it generally suffers from low selectivity and limited understandings on the reaction mechanism. Here, Co<sub>2</sub>@C<sub>3</sub>N<sub>4</sub> nanocomposite has been primarily established through the pyrolysis of dimeric cobalt complex, which mainly constitutes dual-atoms of Co and exhibited exceptional H<sub>2</sub>O<sub>2</sub> production performance, achieving a Faradaic efficiency (FE) of ∼ 90% at −0.4 V vs. RHE and a production rate of 2.38 mol L<sup>−1</sup> g<sub>cat</sub><sup>−1</sup> h<sup>−1</sup>, surpassing most reported SACs in H-cell systems. This enhancement is attributed to the dual site structure of Co and defect-rich interfaces constructed, which promote the O-O bond stabilization and optimize the reactivity/selectivity of H<sub>2</sub>O<sub>2</sub> generation, which was found to be controlled by **OOH generation through an electron coupled proton transfer elementary steps over a proton covered surface.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116646"},"PeriodicalIF":6.5,"publicationDate":"2025-12-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145845450","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 : 2025-12-25DOI: 10.1016/j.jcat.2025.116660
Jian Li , Yaqi Lai , Juan Zhang , Shutao Xu , Sen Wang , Weibin Fan , Wenfu Yan , Zhongmin Liu , Xiangju Meng , Fan Yang , Feng-Shou Xiao
Co-SSZ-39 (Co-AEI) has been considered as efficient catalyst for selective catalytic reduction of nitrogen oxides (NOx) with methane (CH4-SCR), where Co2+ species are proposed as active sites, which are strongly dependent on the sites of Al pair in the zeolite framework, but it is rarely reported yet. Herein, we have prepared three Co-SSZ-39 zeolites from three various zeolite structures (Beta, ZSM-5 and Y) as starting raw materials, exhibiting distinguishable catalytic properties in the CH4-SCR. The Co-SSZ-39-B from Beta zeolite displayed NO conversion at 88 %, which was a little higher than the Co-SSZ-39-Z from ZSM-5 zeolite (82 %), but much higher than Co-SSZ-39-Y from Y zeolite (64 %) at almost the same Co loadings, which are reasonably attributed to their distinguishable Al distribution, i.e. Al pairs, in the zeolite frameworks because ion-exchange of Co2+ into the zeolite requires two negative charges and each Al species can generate one negative charge in the framework. Detailed characterizations showed that the SSZ-39-B and SSZ-39-Z give concentration of Al pair at 70.5 % and 69.8 %, which are much higher than that of SSZ-39-Y (51.8 %). This work demonstrates the importance of zeolite precursors for control of Al sites in the framework zeolites, which offers a new strategy for designing efficient CH4-SCR catalysts in the future.
{"title":"Regulation of Al sites in AEI framework from different zeolite precursors for selective catalytic reduction of NOx with methane","authors":"Jian Li , Yaqi Lai , Juan Zhang , Shutao Xu , Sen Wang , Weibin Fan , Wenfu Yan , Zhongmin Liu , Xiangju Meng , Fan Yang , Feng-Shou Xiao","doi":"10.1016/j.jcat.2025.116660","DOIUrl":"10.1016/j.jcat.2025.116660","url":null,"abstract":"<div><div>Co-SSZ-39 (Co-AEI) has been considered as efficient catalyst for selective catalytic reduction of nitrogen oxides (NO<sub>x</sub>) with methane (CH<sub>4</sub>-SCR), where Co<sup>2+</sup> species are proposed as active sites, which are strongly dependent on the sites of Al pair in the zeolite framework, but it is rarely reported yet. Herein, we have prepared three Co-SSZ-39 zeolites from three various zeolite structures (Beta, ZSM-5 and Y) as starting raw materials, exhibiting distinguishable catalytic properties in the CH<sub>4</sub>-SCR. The Co-SSZ-39-B from Beta zeolite displayed NO conversion at 88 %, which was a little higher than the Co-SSZ-39-Z from ZSM-5 zeolite (82 %), but much higher than Co-SSZ-39-Y from Y zeolite (64 %) at almost the same Co loadings, which are reasonably attributed to their distinguishable Al distribution, <em>i.e.</em> Al pairs, in the zeolite frameworks because ion-exchange of Co<sup>2+</sup> into the zeolite requires two negative charges and each Al species can generate one negative charge in the framework. Detailed characterizations showed that the SSZ-39-B and SSZ-39-Z give concentration of Al pair at 70.5 % and 69.8 %, which are much higher than that of SSZ-39-Y (51.8 %). This work demonstrates the importance of zeolite precursors for control of Al sites in the framework zeolites, which offers a new strategy for designing efficient CH<sub>4</sub>-SCR catalysts in the future.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116660"},"PeriodicalIF":6.5,"publicationDate":"2025-12-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823630","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 : 2025-12-24DOI: 10.1016/j.jcat.2025.116645
Shuang Yan , Yi Liu , Fanyu Wang , Zhaoling Li , Anmin Zheng , Xiao Liu
Achieving high activity for low-temperature catalytic oxidation of chlorinated volatile organic compounds (CVOCs) is often hindered by severe chlorine poisoning and poor stability caused by sluggish chlorine desorption. Herein, a series of alkaline earth metal oxides (AEMOs = MgO, CaO, and SrO)-modified SmMn2O5 (SMO) catalysts were engineered to simultaneously boost stability and low-temperature activity. Electrons spontaneously transferred from AEMOs to SMO due to the higher energy of AEMOs’ highest occupied molecular orbital (HOMO) relative to the lowest unoccupied molecular orbital (LUMO) of SMO. These transferred electrons preferentially populated the anti-bonding orbitals of Mn-O bonds and activated interfacial lattice oxygen, enabling SMO-SrO to achieve T90 for chlorobenzene oxidation at 188 °C (189 °C lower than pristine SMO) and preventing toxic byproduct formation. The intrinsic alkalinity of AEMOs further created additional adsorption and dechlorination sites for chlorobenzene and thus shielded SMO from chlorine poisoning. Notably, SMO-SrO with freedom from chlorine poisoning maintained catalytic activity for over 6000 min even under humid streams (up to 10 vol% H2O). Programming interface electron breaks low-temperature activity and stability tradeoff, precisely guiding the catalysts design for CVOCs oxidation.
{"title":"Breaking activity-stability tradeoff in chlorobenzene catalytic oxidation through interface construction over SmMn2O5","authors":"Shuang Yan , Yi Liu , Fanyu Wang , Zhaoling Li , Anmin Zheng , Xiao Liu","doi":"10.1016/j.jcat.2025.116645","DOIUrl":"10.1016/j.jcat.2025.116645","url":null,"abstract":"<div><div>Achieving high activity for low-temperature catalytic oxidation of chlorinated volatile organic compounds (CVOCs) is often hindered by severe chlorine poisoning and poor stability caused by sluggish chlorine desorption. Herein, a series of alkaline earth metal oxides (AEMOs = MgO, CaO, and SrO)-modified SmMn<sub>2</sub>O<sub>5</sub> (SMO) catalysts were engineered to simultaneously boost stability and low-temperature activity. Electrons spontaneously transferred from AEMOs to SMO due to the higher energy of AEMOs’ highest occupied molecular orbital (HOMO) relative to the lowest unoccupied molecular orbital (LUMO) of SMO. These transferred electrons preferentially populated the anti-bonding orbitals of Mn-O bonds and activated interfacial lattice oxygen, enabling SMO-SrO to achieve T<sub>90</sub> for chlorobenzene oxidation at 188 °C (189 °C lower than pristine SMO) and preventing toxic byproduct formation. The intrinsic alkalinity of AEMOs further created additional adsorption and dechlorination sites for chlorobenzene and thus shielded SMO from chlorine poisoning. Notably, SMO-SrO with freedom from chlorine poisoning maintained catalytic activity for over 6000 min even under humid streams (up to 10 vol% H<sub>2</sub>O). Programming interface electron breaks low-temperature activity and stability tradeoff, precisely guiding the catalysts design for CVOCs oxidation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116645"},"PeriodicalIF":6.5,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823629","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 : 2025-12-23DOI: 10.1016/j.jcat.2025.116659
Yanqi Huang, Xiang Ryan Zhou, Brandon C. Bukowski
Mo/ZSM-5 catalyzes methane dehydroaromatization (MDA), yet the role of entropy on reactive intermediates and transition states remain unresolved. At reaction temperatures of 1000 K, the entropic contributions to the Gibbs free energy of reactive intermediates and transition states are challenging to model and can have consequences for predicting reaction kinetics and steady state coverages. The structure and distribution of active sites during MDA turnovers is complex and here we investigate the simplest ion-exchanged Mo carbide active site in ZSM-5 to isolate how entropy models affect methane activation. We consider two pathways: a C–C coupling pathway that forms ethylene after sequential methane dehydrogenation, and a MoC regeneration pathway that directly forms ethylene then reconstitutes [MoC]2+ sites. The harmonic oscillator approximation and partition function methods that assign hindered translational and rotational motions to low frequency modes were used to compute entropies at 1000 K. We then applied molecular dynamics using a machine learned potential (MLP) to obtain activation free energies for methane activation and hydrogen association via well-tempered metadynamics. Monte Carlo integration using an MLP was used to explicitly calculate translational and rotational entropy contributions for adsorbed methane. By comparing different entropy models, we demonstrate that translational and rotational modes are necessary for weakly adsorbed intermediates. Mean-field microkinetic modeling was used to quantify reaction orders and apparent activation energies for different entropy approximations. On this mononuclear MoC site, C–C coupling of unsaturated carbon intermediates is kinetically favored for direct ethylene formation, and the apparent kinetics depend on the entropy model. This manuscript demonstrates how MLPs in conjunction with enhanced sampling and Monte Carlo integration can inform entropy approaches in a reaction network to be integrated into microkinetic models.
{"title":"Microkinetic modeling of methane activation in Mo/ZSM-5 with machine learning potentials","authors":"Yanqi Huang, Xiang Ryan Zhou, Brandon C. Bukowski","doi":"10.1016/j.jcat.2025.116659","DOIUrl":"10.1016/j.jcat.2025.116659","url":null,"abstract":"<div><div>Mo/ZSM-5 catalyzes methane dehydroaromatization (MDA), yet the role of entropy on reactive intermediates and transition states remain unresolved. At reaction temperatures of 1000 K, the entropic contributions to the Gibbs free energy of reactive intermediates and transition states are challenging to model and can have consequences for predicting reaction kinetics and steady state coverages. The structure and distribution of active sites during MDA turnovers is complex and here we investigate the simplest ion-exchanged Mo carbide active site in ZSM-5 to isolate how entropy models affect methane activation. We consider two pathways: a C–C coupling pathway that forms ethylene after sequential methane dehydrogenation, and a MoC regeneration pathway that directly forms ethylene then reconstitutes [MoC]<sup>2+</sup> sites. The harmonic oscillator approximation and partition function methods that assign hindered translational and rotational motions to low frequency modes were used to compute entropies at 1000 K. We then applied molecular dynamics using a machine learned potential (MLP) to obtain activation free energies for methane activation and hydrogen association via well-tempered metadynamics. Monte Carlo integration using an MLP was used to explicitly calculate translational and rotational entropy contributions for adsorbed methane. By comparing different entropy models, we demonstrate that translational and rotational modes are necessary for weakly adsorbed intermediates. Mean-field microkinetic modeling was used to quantify reaction orders and apparent activation energies for different entropy approximations. On this mononuclear MoC site, C–C coupling of unsaturated carbon intermediates is kinetically favored for direct ethylene formation, and the apparent kinetics depend on the entropy model. This manuscript demonstrates how MLPs in conjunction with enhanced sampling and Monte Carlo integration can inform entropy approaches in a reaction network to be integrated into microkinetic models.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"454 ","pages":"Article 116659"},"PeriodicalIF":6.5,"publicationDate":"2025-12-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813456","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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