Pub Date : 2026-03-15Epub Date: 2026-02-12DOI: 10.1016/j.mcat.2026.115795
Liye Bao , Lihui Shi , Xinqian Fang , Yifan Zhao , Haijun Chen , Yongtao Xia
Durable ammonia selective catalytic reduction (NH3-SCR) catalysts that retain activity under extreme hydrothermal conditions are essential to reduce lifecycle emissions and catalyst replacement frequency in diesel aftertreatment. We report a process-intensified interzeolite transformation route that utilizes low-silica, platelet-like FER zeolite as the aluminum source. This route synthesizes high-silica, thin-platelet SSZ-39 (AEI) at 170 °C, achieving high crystallinity within 8 h under optimized conditions. Time-resolved XRD, TG–DSC, FT-IR, and SEM suggest that AEI formation proceeds through alkaline hydrolysis and reconstruction of labile single five-membered ring (S5R) units inherited from FER. Cu/AEI catalysts derived from FER and FAU precursors with comparable Si/Al ratios and Cu loadings were evaluated for NH3-SCR and durability. After severe hydrothermal aging at 900 °C for 6 h, the FER-derived catalyst maintains substantially higher NOx conversion than its FAU-derived counterpart and exhibits mitigated N2O formation at high temperature. Spectroscopic analyses link this resilience to a higher retained fraction of paired framework Al in the FER-derived zeolite, which stabilizes Cu2+-2Z species and suppresses aggregation into CuOx clusters during aging. These findings demonstrate that precursor-enabled Al distribution control via interzeolite transformation offers an engineering-relevant strategy to improve the durability and environmental performance of Cu/AEI SCR catalysts.
{"title":"Interzeolite transformation of FER into thin-platelet SSZ-39 for highly hydrothermally stable Cu-based NH3-SCR catalysts","authors":"Liye Bao , Lihui Shi , Xinqian Fang , Yifan Zhao , Haijun Chen , Yongtao Xia","doi":"10.1016/j.mcat.2026.115795","DOIUrl":"10.1016/j.mcat.2026.115795","url":null,"abstract":"<div><div>Durable ammonia selective catalytic reduction (NH<sub>3</sub>-SCR) catalysts that retain activity under extreme hydrothermal conditions are essential to reduce lifecycle emissions and catalyst replacement frequency in diesel aftertreatment. We report a process-intensified interzeolite transformation route that utilizes low-silica, platelet-like FER zeolite as the aluminum source. This route synthesizes high-silica, thin-platelet SSZ-39 (AEI) at 170 °C, achieving high crystallinity within 8 h under optimized conditions. Time-resolved XRD, TG–DSC, FT-IR, and SEM suggest that AEI formation proceeds through alkaline hydrolysis and reconstruction of labile single five-membered ring (S5R) units inherited from FER. Cu/AEI catalysts derived from FER and FAU precursors with comparable Si/Al ratios and Cu loadings were evaluated for NH<sub>3</sub>-SCR and durability. After severe hydrothermal aging at 900 °C for 6 h, the FER-derived catalyst maintains substantially higher NO<sub>x</sub> conversion than its FAU-derived counterpart and exhibits mitigated N<sub>2</sub>O formation at high temperature. Spectroscopic analyses link this resilience to a higher retained fraction of paired framework Al in the FER-derived zeolite, which stabilizes Cu<sup>2+</sup>-2Z species and suppresses aggregation into CuO<sub>x</sub> clusters during aging. These findings demonstrate that precursor-enabled Al distribution control via interzeolite transformation offers an engineering-relevant strategy to improve the durability and environmental performance of Cu/AEI SCR catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115795"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186413","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 : 2026-03-15Epub Date: 2026-02-11DOI: 10.1016/j.mcat.2026.115793
Yongning Ma , Zengyuan An , Kuan Wang , Enzhou Liu , Xiaolong Li
Photoelectrochemical cathodic protection (PECCP) has emerged as a promising approach for mitigating metal corrosion. However, the rapid consumption of sacrificial metals and high cost associated with conventional PECCP systems limit their practical applications. To overcome the limitations of metals protection in PECCP technology, a NiCoP/g-C3N4 composite with an interfacial Schottky heterojunction was fabricated to replace active metals via a simple one-pot method. Various characterizations confirm the establishment of an interfacial Schottky heterojunction between NiCoP and CN. Furthermore, inspired by efficient electron transfer mechanisms observed in hydrogen evolution reactions, the composite material was applied for the first time to anti-corrosion protection. The prepared composites were employed as a photoanode material for PECCP to resist corrosion of Q235 steels. Corrosion rate of the 75-NCP/CN composite was measured to 15.93 g·year−1·m−2, significantly lower than those of control groups. Under constant temperature and humidity system, the corrosion resistance gradually increases from far to near the center of the coated catalyst. This outstanding corrosion resistance is attributed to the excellent charge separation efficiency of the NiCoP/g-C3N4 Schottky interface and the excited electron transfer to the metal substrate rapidly driven by a favorable potential difference. This work presents a viable design concept for constructing high-performance and long-term stable g-C3N4-based photoanodes.
{"title":"Establish NiCoP/g-C3N4 Schottky heterojunction to promote spatial charge separation rate for steels protection and mechanism analysis","authors":"Yongning Ma , Zengyuan An , Kuan Wang , Enzhou Liu , Xiaolong Li","doi":"10.1016/j.mcat.2026.115793","DOIUrl":"10.1016/j.mcat.2026.115793","url":null,"abstract":"<div><div>Photoelectrochemical cathodic protection (PECCP) has emerged as a promising approach for mitigating metal corrosion. However, the rapid consumption of sacrificial metals and high cost associated with conventional PECCP systems limit their practical applications. To overcome the limitations of metals protection in PECCP technology, a NiCoP/g-C<sub>3</sub>N<sub>4</sub> composite with an interfacial Schottky heterojunction was fabricated to replace active metals via a simple one-pot method. Various characterizations confirm the establishment of an interfacial Schottky heterojunction between NiCoP and CN. Furthermore, inspired by efficient electron transfer mechanisms observed in hydrogen evolution reactions, the composite material was applied for the first time to anti-corrosion protection. The prepared composites were employed as a photoanode material for PECCP to resist corrosion of Q235 steels. Corrosion rate of the 75-NCP/CN composite was measured to 15.93 <em>g</em>·year<sup>−1</sup>·m<sup>−2</sup>, significantly lower than those of control groups. Under constant temperature and humidity system, the corrosion resistance gradually increases from far to near the center of the coated catalyst. This outstanding corrosion resistance is attributed to the excellent charge separation efficiency of the NiCoP/g-C<sub>3</sub>N<sub>4</sub> Schottky interface and the excited electron transfer to the metal substrate rapidly driven by a favorable potential difference. This work presents a viable design concept for constructing high-performance and long-term stable g-C<sub>3</sub>N<sub>4</sub>-based photoanodes.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115793"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186478","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 : 2026-03-15Epub Date: 2026-02-07DOI: 10.1016/j.mcat.2026.115780
Deniz Akgül , Halil Bilgin , Yuxin Zhao , Alper Uzun , Viktorya Aviyente
In zeolites, the acidic protons are known to migrate across the catalytic framework, and this proton mobility can influence the reactivity of the metal centers anchored within the structure as well. In this study, we employed density functional theory (DFT) calculations to investigate the effects of proton reverse spillover on the ligand-exchange mechanisms of atomically dispersed Rh(CO)2 complexes supported on HY zeolite. Particular emphasis was placed on the role of the reverse proton spillover in facilitating the exchange of CO ligands with gas-phase acetylene. The free energy activation barrier (ΔG≠) for proton reverse spillover from the zeolite surface to the Rh center in Rh(CO)2/zeolite is relatively high (19.4 kcal/mol). As acetylene coordinates to the metal, however, the barrier decreases significantly (9.3 kcal/mol), indicating that coordination of C2H2 to Rh promotes proton transfer. Once CO dissociation occurs to give Rh(CO)(C2H2)/zeolite, reverse proton spillover from the surface becomes less favorable, with a barrier of 26.7 kcal/mol. Finally, for the fully substituted Rh(C2H2)2 species, reverse proton migration from the surface to the metal is essentially prohibited due to the very high barrier (44.4 kcal/mol). These results highlight the strong coupling between ligand exchange and proton mobility in zeolite-supported Rh complexes, underscoring how the local coordination environment dynamically tunes the feasibility of proton transfer.
{"title":"DFT studies for ligand modification and proton spillover zeolite supported Rh(CO)2 complex","authors":"Deniz Akgül , Halil Bilgin , Yuxin Zhao , Alper Uzun , Viktorya Aviyente","doi":"10.1016/j.mcat.2026.115780","DOIUrl":"10.1016/j.mcat.2026.115780","url":null,"abstract":"<div><div>In zeolites, the acidic protons are known to migrate across the catalytic framework, and this proton mobility can influence the reactivity of the metal centers anchored within the structure as well. In this study, we employed density functional theory (DFT) calculations to investigate the effects of proton reverse spillover on the ligand-exchange mechanisms of atomically dispersed Rh(CO)<sub>2</sub> complexes supported on HY zeolite. Particular emphasis was placed on the role of the reverse proton spillover in facilitating the exchange of CO ligands with gas-phase acetylene. The free energy activation barrier (ΔG<sup>≠</sup>) for proton reverse spillover from the zeolite surface to the Rh center in Rh(CO)<sub>2</sub>/zeolite is relatively high (19.4 kcal/mol). As acetylene coordinates to the metal, however, the barrier decreases significantly <strong>(</strong>9.3 kcal/mol), indicating that coordination of C<sub>2</sub>H<sub>2</sub> to Rh promotes proton transfer. Once CO dissociation occurs to give Rh(CO)(C<sub>2</sub>H<sub>2</sub>)/zeolite<strong>,</strong> reverse proton spillover from the surface becomes less favorable, with a barrier of 26.7 kcal/mol<strong>.</strong> Finally, for the fully substituted Rh(C<sub>2</sub>H<sub>2</sub>)<sub>2</sub> species, reverse proton migration from the surface to the metal is essentially prohibited due to the very high barrier (44.4 kcal/mol). These results highlight the strong coupling between ligand exchange and proton mobility in zeolite-supported Rh complexes, underscoring how the local coordination environment dynamically tunes the feasibility of proton transfer.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115780"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186505","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 : 2026-03-15Epub Date: 2026-02-04DOI: 10.1016/j.mcat.2026.115772
Chuanhua Li , Yubao Shi, Linxia Chen, Ziheng Wang, Wei Xiao, Xuemin Yan
Electrolysis of water to produce hydrogen can alleviate the problem of global energy shortage, and seeking efficient water splitting electrocatalysts is the promising direction. In this work, Cr-doped nickel oxalate (Cr-NiC2O4/NF) was synthesized on nickel foam (NF) by a one-step hydrothermal method and used as an alkaline electrolytic water catalyst. The electrocatalytic activity of NiC2O4 is significantly improved by Cr doping. For the oxygen evolution reaction (OER), the overpotential is 324 mV at 100 mA cm-2, and for the hydrogen evolution reaction (HER), the overpotential is 191 mV at 10 mA cm-2. When Cr-NiC2O4/NF is used as anode and cathode in water splitting, only voltage of 1.58 V is required at current density of 10 mA cm-2. Furthermore, the mechanism of enhanced catalytic activity via surface reconstruction during the OER and HER was systematically studied. The pre-catalyst Cr-NiC2O4 was restructured into hydroxides and hydroxyl oxides for OER, and some Cr-NiC2O4 was converted into hydroxides for HER. Consequently, this investigation provides a new method to improve the electrocatalytic performance of metal oxalates and a theoretical guidance for surface reconstruction.
电解水制氢可以缓解全球能源短缺的问题，寻求高效的水分解电催化剂是有希望的方向。本文采用一步水热法在泡沫镍（NF）上合成了掺杂cr的草酸镍（Cr-NiC2O4/NF），并将其用作碱性电解水催化剂。Cr的掺杂显著提高了NiC2O4的电催化活性。析氧反应（OER）在100 mA cm-2时的过电位为324 mV，析氢反应（HER）在10 mA cm-2时的过电位为191 mV。当Cr-NiC2O4/NF作为水分解的阳极和阴极时，在电流密度为10 mA cm-2时，只需要1.58 V的电压。此外，系统地研究了OER和HER过程中通过表面重构提高催化活性的机理。预催化剂Cr-NiC2O4被重组为氢氧化物和羟基氧化物用于OER，部分Cr-NiC2O4被转化为氢氧化物用于HER。因此，本研究为提高金属草酸盐的电催化性能提供了一种新的方法，并为表面重建提供了理论指导。
{"title":"The enhanced electrocatalytic activity of Cr-doped NiC2O4 for water splitting via surface reconstruction","authors":"Chuanhua Li , Yubao Shi, Linxia Chen, Ziheng Wang, Wei Xiao, Xuemin Yan","doi":"10.1016/j.mcat.2026.115772","DOIUrl":"10.1016/j.mcat.2026.115772","url":null,"abstract":"<div><div>Electrolysis of water to produce hydrogen can alleviate the problem of global energy shortage, and seeking efficient water splitting electrocatalysts is the promising direction. In this work, Cr-doped nickel oxalate (Cr-NiC<sub>2</sub>O<sub>4</sub>/NF) was synthesized on nickel foam (NF) by a one-step hydrothermal method and used as an alkaline electrolytic water catalyst. The electrocatalytic activity of NiC<sub>2</sub>O<sub>4</sub> is significantly improved by Cr doping. For the oxygen evolution reaction (OER), the overpotential is 324 mV at 100 mA cm<sup>-2</sup>, and for the hydrogen evolution reaction (HER), the overpotential is 191 mV at 10 mA cm<sup>-2</sup>. When Cr-NiC<sub>2</sub>O<sub>4</sub>/NF is used as anode and cathode in water splitting, only voltage of 1.58 V is required at current density of 10 mA cm<sup>-2</sup>. Furthermore, the mechanism of enhanced catalytic activity via surface reconstruction during the OER and HER was systematically studied. The pre-catalyst Cr-NiC<sub>2</sub>O<sub>4</sub> was restructured into hydroxides and hydroxyl oxides for OER, and some Cr-NiC<sub>2</sub>O<sub>4</sub> was converted into hydroxides for HER. Consequently, this investigation provides a new method to improve the electrocatalytic performance of metal oxalates and a theoretical guidance for surface reconstruction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115772"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186167","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 : 2026-03-15Epub Date: 2026-02-11DOI: 10.1016/j.mcat.2026.115800
Adnaildo Miranda Mota , Raiane Macedo dos Santos , José Felipe dos Santos , Marcus Vinicius Santos da Silva , Luiza A. Mercante , Luciana Almeida Silva
Advances in solar-driven hydrogen production rely heavily on the design of photocatalysts that maximize utilization of visible light while minimizing charge recombination. Despite significant progress in semiconductor-based photocatalysis, achieving high efficiency with low CdS loading remains challenging. Here, we introduce a hybrid strategy combining electrospinning and sonochemical deposition to produce a highly efficient CdS/ZnO heterostructure with enhanced activity. Electrospun ZnO nanofibers decorated with CdS nanoparticles (CdS@ZnO NFs) were successfully synthesized via a sonochemical-assisted deposition method and evaluated as photocatalysts for H2 production under simulated sunlight. Structural, morphological, and spectroscopic analyses confirmed the formation of a well-defined CdS/ZnO heterostructure. Compared with pristine CdS and ZnO NFs, the composite exhibited enhanced optical absorption, favorable band-edge alignment, and more efficient charge separation, as indicated by its superior photocurrent response. The CdS@ZnO NFs achieved an exceptional hydrogen evolution rate of 13.4 mmol g−1 h−1, outperforming pristine CdS by more than threefold and surpassing most previously reported ZnO/CdS systems. The composite also demonstrated remarkable photostability over three consecutive cycles, whereas pure CdS rapidly deactivated due to photocorrosion. The enhanced activity and durability are attributed to the one-dimensional nanofibrous architecture and to an S-scheme–like charge-transfer behavior at the CdS/ZnO interface, which promotes effective charge separation while preserving strong redox capability. These results highlight interfacial engineering in CdS/ZnO nanofibers as a promising strategy for developing efficient photocatalysts for solar-driven hydrogen production.
{"title":"CdS/ZnO electrospun nanofiber heterostructure for efficient solar-driven hydrogen production","authors":"Adnaildo Miranda Mota , Raiane Macedo dos Santos , José Felipe dos Santos , Marcus Vinicius Santos da Silva , Luiza A. Mercante , Luciana Almeida Silva","doi":"10.1016/j.mcat.2026.115800","DOIUrl":"10.1016/j.mcat.2026.115800","url":null,"abstract":"<div><div>Advances in solar-driven hydrogen production rely heavily on the design of photocatalysts that maximize utilization of visible light while minimizing charge recombination. Despite significant progress in semiconductor-based photocatalysis, achieving high efficiency with low CdS loading remains challenging. Here, we introduce a hybrid strategy combining electrospinning and sonochemical deposition to produce a highly efficient CdS/ZnO heterostructure with enhanced activity. Electrospun ZnO nanofibers decorated with CdS nanoparticles (CdS@ZnO NFs) were successfully synthesized via a sonochemical-assisted deposition method and evaluated as photocatalysts for H<sub>2</sub> production under simulated sunlight. Structural, morphological, and spectroscopic analyses confirmed the formation of a well-defined CdS/ZnO heterostructure. Compared with pristine CdS and ZnO NFs, the composite exhibited enhanced optical absorption, favorable band-edge alignment, and more efficient charge separation, as indicated by its superior photocurrent response. The CdS@ZnO NFs achieved an exceptional hydrogen evolution rate of 13.4 mmol g<sup>−1</sup> h<sup>−1</sup>, outperforming pristine CdS by more than threefold and surpassing most previously reported ZnO/CdS systems. The composite also demonstrated remarkable photostability over three consecutive cycles, whereas pure CdS rapidly deactivated due to photocorrosion. The enhanced activity and durability are attributed to the one-dimensional nanofibrous architecture and to an S-scheme–like charge-transfer behavior at the CdS/ZnO interface, which promotes effective charge separation while preserving strong redox capability. These results highlight interfacial engineering in CdS/ZnO nanofibers as a promising strategy for developing efficient photocatalysts for solar-driven hydrogen production.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115800"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186475","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 : 2026-03-15Epub Date: 2026-02-13DOI: 10.1016/j.mcat.2026.115806
Abdulaziz A.M. Abahussain , Norah Alwadai , Hamid Ahmed , Ghzzai Almutairi , Fekri Abdulraqeb Ahmed Ali , Khaled M. Banabdwin , Alaaddin M.M. Saeed , Ahmed E. Abasaeed , Rawesh Kumar , Ahmed S. Al-Fatesh
Development of a catalyst for partial oxidation of methane (POM) is preferred over total oxidation of methane (TOM), as the POM yielded hydrogen-rich syngas, which is a typical precursor in chemical synthesis. The 5Ni/8YZr catalyst exhibits 51 % H2 yield and 25 % CO2 conversion at 600 °C showing more selectivity to POM than total combustion. An H2/CO ratio of >2.75 further suggests the participation of indirect pathways of POM. The promotional effect of 0.5–2 wt.% Sm is studied over 5Ni/8YZr. The catalysts are characterized by X-ray diffraction study, temperature programmed reduction/oxidation experiment, surface area and porosity results, X-ray photoelectron spectroscopy, thermogravimetry, and Raman spectroscopy. Sm promotion significantly enhances the oxide concentration over the catalyst surface, whereas 0.5–1 wt.% Sm brings a noticeable change in the electronic environment that is a negative charge deficit in the vicinity of Ni and negative charge enrichment about Zr and Y. At 600 °C, 0.5 wt.% Sm-promoted catalyst achieves 67–69 % H2 yield at 14,400 mL h⁻¹ g⁻¹ GHSV during 300 min time on stream (TOS) and >75 % H2 yield at 5400 mL h⁻¹ g⁻¹, GHSV up to 24 h TOS. The current finding puts the Sm-Ni system at the centre of research for achieving hydrogen-rich syngas through the POM reaction.
{"title":"Samarium promoted Ni-catalyst dispersed over yttria-zirconia for H2-rich syngas production through partial oxidation of methane","authors":"Abdulaziz A.M. Abahussain , Norah Alwadai , Hamid Ahmed , Ghzzai Almutairi , Fekri Abdulraqeb Ahmed Ali , Khaled M. Banabdwin , Alaaddin M.M. Saeed , Ahmed E. Abasaeed , Rawesh Kumar , Ahmed S. Al-Fatesh","doi":"10.1016/j.mcat.2026.115806","DOIUrl":"10.1016/j.mcat.2026.115806","url":null,"abstract":"<div><div>Development of a catalyst for partial oxidation of methane (POM) is preferred over total oxidation of methane (TOM), as the POM yielded hydrogen-rich syngas, which is a typical precursor in chemical synthesis. The 5Ni/8YZr catalyst exhibits 51 % H<sub>2</sub> yield and 25 % CO<sub>2</sub> conversion at 600 °C showing more selectivity to POM than total combustion. An H<sub>2</sub>/CO ratio of >2.75 further suggests the participation of indirect pathways of POM. The promotional effect of 0.5–2 wt.% Sm is studied over 5Ni/8YZr. The catalysts are characterized by X-ray diffraction study, temperature programmed reduction/oxidation experiment, surface area and porosity results, X-ray photoelectron spectroscopy, thermogravimetry, and Raman spectroscopy. Sm promotion significantly enhances the oxide concentration over the catalyst surface, whereas 0.5–1 wt.% Sm brings a noticeable change in the electronic environment that is a negative charge deficit in the vicinity of Ni and negative charge enrichment about Zr and Y. At 600 °C, 0.5 wt.% Sm-promoted catalyst achieves 67–69 % H<sub>2</sub> yield at 14,400 mL h⁻¹ g⁻¹ GHSV during 300 min time on stream (TOS) and >75 % H<sub>2</sub> yield at 5400 mL h⁻¹ g⁻¹, GHSV up to 24 h TOS. The current finding puts the Sm-Ni system at the centre of research for achieving hydrogen-rich syngas through the POM reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115806"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186484","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 efficient conversion of carbon dioxide (CO2) into value-added chemicals is crucial for sustainable development. Herein, we designed and synthesized a series of NiCo/NiCo-OH@NC-T catalysts via a hydrothermal-pyrolysis method for the N-formylation of amines with CO2 and H2. The relationship between their structure, activity, and the reaction mechanism was systematically investigated. Comprehensive characterization revealed that the pyrolysis temperature critically modulates the surface composition, finely tuning the ratio between metallic (Ni/Co) and hydroxide NiCo-OH species. The optimal NiCo/NiCo-OH@NC-450 catalyst, which features a balanced metal-hydroxide species and strong bimetallic synergy, demonstrated exceptional performance in the model reaction with morpholine, achieving complete conversion and 96% selectivity. A distinct volcano-shaped correlation was observed between catalytic activity and pyrolysis temperature, which is directly linked to the catalyst's hydrogen activation capacity and CO2 adsorption strength. Mechanistic studies, including in situ DRIFTS, identified a surface-adsorbed formate (HCOO*) as the pivotal C1 intermediate, providing direct evidence for the reaction pathway. This work underscores the significance of engineering multifunctional interfaces in bifunctional catalysts for efficient CO2 hydrogenation and provides fundamental insights into the underlying structure-activity relationship.
{"title":"Selective N-Formylation of amines using CO2 and H2 over NiCo Bimetallic Catalysts with Tunable Metal-Metal Hydroxide Species","authors":"Jinlei Li, Dong Yun, Jian Yang, Yongcheng Lan, Qiren Liu, Chuanzhi Xu, Jianhua Liu, Chungu Xia","doi":"10.1016/j.mcat.2026.115770","DOIUrl":"10.1016/j.mcat.2026.115770","url":null,"abstract":"<div><div>The efficient conversion of carbon dioxide (CO<sub>2</sub>) into value-added chemicals is crucial for sustainable development. Herein, we designed and synthesized a series of NiCo/NiCo-OH@NC-T catalysts via a hydrothermal-pyrolysis method for the N-formylation of amines with CO<sub>2</sub> and H<sub>2</sub>. The relationship between their structure, activity, and the reaction mechanism was systematically investigated. Comprehensive characterization revealed that the pyrolysis temperature critically modulates the surface composition, finely tuning the ratio between metallic (Ni/Co) and hydroxide NiCo-OH species. The optimal NiCo/NiCo-OH@NC-450 catalyst, which features a balanced metal-hydroxide species and strong bimetallic synergy, demonstrated exceptional performance in the model reaction with morpholine, achieving complete conversion and 96% selectivity. A distinct volcano-shaped correlation was observed between catalytic activity and pyrolysis temperature, which is directly linked to the catalyst's hydrogen activation capacity and CO<sub>2</sub> adsorption strength. Mechanistic studies, including in situ DRIFTS, identified a surface-adsorbed formate (HCOO*) as the pivotal C1 intermediate, providing direct evidence for the reaction pathway. This work underscores the significance of engineering multifunctional interfaces in bifunctional catalysts for efficient CO<sub>2</sub> hydrogenation and provides fundamental insights into the underlying structure-activity relationship.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115770"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186506","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 : 2026-03-15Epub Date: 2026-02-12DOI: 10.1016/j.mcat.2026.115791
Daniel Omoding , Devyani Srivastava , Pramod Kumar , Om Prakash , Ravindra K. Gupta , Ahamad Imran , Zia-Ul-Sabah , Abhinav Kumar
The high cost, limited abundance and wide industrial demand for noble metals drive the search for inexpensive and efficient non-noble metal electrocatalysts for oxygen/hydrogen evolution reactions (O/HERs) to meet global clean energy needs. Herein, three isomeric N-benzyl-1-(o/m/p-substituted hydroxyphenyl)dithiocarbamate appended Ni(II) complexes viz. [Ni(S2CN(CH2C6H5)(CH2C6H4-o-OH))(dppe)][PF6] (1), [Ni(S2CN(CH2C6H5)(CH2C6H4-m-OH))(dppe)][PF6] (2) and [Ni(S2CN(CH2C6H5)(CH2C6H4-p-OH))(dppe)][PF6] (3) have been synthesized and solvothermally decomposed in oleylamine to engender nickel sulfide/phosphide composites: NiS-2BA, NiS-3BA and NiS-4BA, respectively. The compositions of the decomposed materials are identified using PXRD studies as; Ni7S6 (NiS-2BA), Ni7S6/NiP (NiS-3BA) and Ni7S6/NiP/Ni8P3 (NiS-4BA), which have further been substantiated using FESEM-EDS, HRTEM-SAED and XPS analysis. These materials showcase promising bifunctional activity for OER/HER in basic/acidic media. NiS-4BA demonstrates the best activity since it exhibits the lowest Tafel slopes and highest current densities for both OER (117 mV·dec‑1; 43.2 mA·cm-2) and HER (136 mV·dec‑1; 72.4 mA·cm-2) at 20 mV·s-1. This good electrocatalytic activity arises from its small particle size, high electrochemical surface area, and synergistic multiphase composition. Overall, this study establishes that the positional isomeric phenolic –OH group on the ligand governs the phase evolution, morphology, and particle size, leading to the formation of tunable multiphase Ni7S6/NiP/Ni8P3 composites with enhanced and promising bifunctional OER/HER catalytic performance.
{"title":"Tailoring nickel sulfide/nickel phosphide composites derived from dppe-based Ni(II) dithiocarbamates for efficient bifunctional OER–HER electrocatalysis","authors":"Daniel Omoding , Devyani Srivastava , Pramod Kumar , Om Prakash , Ravindra K. Gupta , Ahamad Imran , Zia-Ul-Sabah , Abhinav Kumar","doi":"10.1016/j.mcat.2026.115791","DOIUrl":"10.1016/j.mcat.2026.115791","url":null,"abstract":"<div><div>The high cost, limited abundance and wide industrial demand for noble metals drive the search for inexpensive and efficient non-noble metal electrocatalysts for oxygen/hydrogen evolution reactions (O/HERs) to meet global clean energy needs. Herein, three isomeric <em>N</em>-benzyl-1-(<em>o/m/p</em>-substituted hydroxyphenyl)dithiocarbamate appended Ni(II) complexes <em>viz.</em> [Ni(S<sub>2</sub>CN(CH<sub>2</sub>C<sub>6</sub>H<sub>5</sub>)(CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>-<em>o</em>-OH))(dppe)][PF<sub>6</sub>] (<strong>1</strong>), [Ni(S<sub>2</sub>CN(CH<sub>2</sub>C<sub>6</sub>H<sub>5</sub>)(CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>-<em>m</em>-OH))(dppe)][PF<sub>6</sub>] (<strong>2</strong>) and [Ni(S<sub>2</sub>CN(CH<sub>2</sub>C<sub>6</sub>H<sub>5</sub>)(CH<sub>2</sub>C<sub>6</sub>H<sub>4</sub>-<em>p</em>-OH))(dppe)][PF<sub>6</sub>] (<strong>3</strong>) have been synthesized and solvothermally decomposed in oleylamine to engender nickel sulfide/phosphide composites: <strong>NiS-2BA, NiS-3BA</strong> and <strong>NiS-4BA</strong>, respectively. The compositions of the decomposed materials are identified using PXRD studies as; Ni<sub>7</sub>S<sub>6</sub> (<strong>NiS-2BA</strong>), Ni<sub>7</sub>S<sub>6</sub>/NiP (<strong>NiS-3BA</strong>) and Ni<sub>7</sub>S<sub>6</sub>/NiP/Ni<sub>8</sub>P<sub>3</sub> (<strong>NiS-4BA</strong>), which have further been substantiated using FESEM-EDS, HRTEM-SAED and XPS analysis. These materials showcase promising bifunctional activity for OER/HER in basic/acidic media. <strong>NiS-4BA</strong> demonstrates the best activity since it exhibits the lowest Tafel slopes and highest current densities for both OER (117 mV·dec<sup>‑1</sup>; 43.2 mA·cm<sup>-2</sup>) and HER (136 mV·dec<sup>‑1</sup>; 72.4 mA·cm<sup>-2</sup>) at 20 mV·s<sup>-1</sup>. This good electrocatalytic activity arises from its small particle size, high electrochemical surface area, and synergistic multiphase composition. Overall, this study establishes that the positional isomeric phenolic –OH group on the ligand governs the phase evolution, morphology, and particle size, leading to the formation of tunable multiphase Ni<sub>7</sub>S<sub>6</sub>/NiP/Ni<sub>8</sub>P<sub>3</sub> composites with enhanced and promising bifunctional OER/HER catalytic performance.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115791"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186480","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 : 2026-03-15Epub Date: 2026-02-05DOI: 10.1016/j.mcat.2026.115782
Rui Sui , Yishan Gao , Bo Peng
1,2-Dichloroethane (1,2-DCE) is recognized as a recalcitrant and environmentally hazardous compound. In this study, we synthesized Ru single-atom catalyst supported on mesoporous flake-like Al2O3 (Ru1/Al2O3) to facilitate the catalytic degradation of 1,2-DCE. The Ru1/Al2O3 exhibited notably lower temperatures for 50% and 90% conversion (T50 and T90) at 229 °C and 294 °C, respectively, compared to Ru nanoparticles supported on Al2O3 (Ru NP/Al2O3) with T50 and T90 values of 285 °C and 357 °C, and pure Al2O3, which showed values of 328 °C and 399 °C. Additionally, the Ru1/Al2O3 demonstrated superior resistance to chlorine poisoning and maintained stability in the presence of water during durability assessments. Multiple characterization experiments have demonstrated that the Ru1/Al2O3 catalyst exhibited pronounced redox and substantial acidity, which contributed to the enhanced production yields of CO2 and HCl. Computational simulations further revealed that the Ru single-atom active sites substantially enhance the selectivity of 1,2-DCE degradation relative to the Ru (0001) surface and the formation of Ru1−O5 sites. These findings provide valuable insights for the advancement of efficient single-atom catalysts aimed at the remediation of industrial pollutants.
{"title":"Enhanced catalytic combustion of 1,2-dichloroethane over Ru1/Al2O3 catalyst via regulating the Ru−O bond","authors":"Rui Sui , Yishan Gao , Bo Peng","doi":"10.1016/j.mcat.2026.115782","DOIUrl":"10.1016/j.mcat.2026.115782","url":null,"abstract":"<div><div>1,2-Dichloroethane (1,2-DCE) is recognized as a recalcitrant and environmentally hazardous compound. In this study, we synthesized Ru single-atom catalyst supported on mesoporous flake-like Al<sub>2</sub>O<sub>3</sub> (Ru<sub>1</sub>/Al<sub>2</sub>O<sub>3</sub>) to facilitate the catalytic degradation of 1,2-DCE. The Ru<sub>1</sub>/Al<sub>2</sub>O<sub>3</sub> exhibited notably lower temperatures for 50% and 90% conversion (<em>T</em><sub>50</sub> and <em>T</em><sub>90</sub>) at 229 °C and 294 °C, respectively, compared to Ru nanoparticles supported on Al<sub>2</sub>O<sub>3</sub> (Ru NP/Al<sub>2</sub>O<sub>3</sub>) with <em>T</em><sub>50</sub> and <em>T</em><sub>90</sub> values of 285 °C and 357 °C, and pure Al<sub>2</sub>O<sub>3</sub>, which showed values of 328 °C and 399 °C. Additionally, the Ru<sub>1</sub>/Al<sub>2</sub>O<sub>3</sub> demonstrated superior resistance to chlorine poisoning and maintained stability in the presence of water during durability assessments. Multiple characterization experiments have demonstrated that the Ru<sub>1</sub>/Al<sub>2</sub>O<sub>3</sub> catalyst exhibited pronounced redox and substantial acidity, which contributed to the enhanced production yields of CO<sub>2</sub> and HCl. Computational simulations further revealed that the Ru single-atom active sites substantially enhance the selectivity of 1,2-DCE degradation relative to the Ru (0001) surface and the formation of Ru<sub>1</sub>−O<sub>5</sub> sites. These findings provide valuable insights for the advancement of efficient single-atom catalysts aimed at the remediation of industrial pollutants.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115782"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186504","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 : 2026-03-15Epub Date: 2026-02-14DOI: 10.1016/j.mcat.2026.115804
Pablo F. Corregidor, Delicia E. Acosta
Understanding how the structural environment of Brønsted acid sites governs catalytic performance remains a central challenge in zeolite catalysis. In this work, we investigate a series of H-ZSM-5 zeolites with systematically varied Si/Al ratios (Z-11, Z-12, Z-20, Z-80, and Z-140) as catalysts for the transesterification of vinyl acetate with isoamyl alcohol. By combining pyridine FT-IR spectroscopy, BET surface analysis, time-resolved catalytic measurements, and intrinsic turnover frequency (TOF) analysis, we critically assess the relevance of commonly used acidity descriptors.
The results show that total Brønsted acid site density and strong-site fractions derived from pyridine desorption are insufficient to rationalize catalytic activity trends across the series. In contrast, intrinsic TOF values reveal a strong dependence of catalytic performance on Brønsted acid site strength, which increases markedly with increasing Si/Al ratio due to enhanced aluminum isolation. High-Si zeolites, despite their lower acid site density, exhibit significantly higher intrinsic activity, highlighting the dominant role of site strength over site population.
The combined interpretation of spectroscopic acidity data, intrinsic kinetics, and catalytic performance demonstrates that catalytic behavior arises from a balance between Brønsted site strength, effective site population, and confinement effects within the MFI framework. These findings provide a physically consistent basis for interpreting structure–acidity–activity relationships in Brønsted-acid-mediated reactions over microporous zeolites.
{"title":"Structure–acidity–activity relationships in H-ZSM-5: Insights from acidity, TOF, and time-resolved catalysis","authors":"Pablo F. Corregidor, Delicia E. Acosta","doi":"10.1016/j.mcat.2026.115804","DOIUrl":"10.1016/j.mcat.2026.115804","url":null,"abstract":"<div><div>Understanding how the structural environment of Brønsted acid sites governs catalytic performance remains a central challenge in zeolite catalysis. In this work, we investigate a series of H-ZSM-5 zeolites with systematically varied Si/Al ratios (Z-11, Z-12, Z-20, Z-80, and Z-140) as catalysts for the transesterification of vinyl acetate with isoamyl alcohol. By combining pyridine FT-IR spectroscopy, BET surface analysis, time-resolved catalytic measurements, and intrinsic turnover frequency (TOF) analysis, we critically assess the relevance of commonly used acidity descriptors.</div><div>The results show that total Brønsted acid site density and strong-site fractions derived from pyridine desorption are insufficient to rationalize catalytic activity trends across the series. In contrast, intrinsic TOF values reveal a strong dependence of catalytic performance on Brønsted acid site strength, which increases markedly with increasing Si/Al ratio due to enhanced aluminum isolation. High-Si zeolites, despite their lower acid site density, exhibit significantly higher intrinsic activity, highlighting the dominant role of site strength over site population.</div><div>The combined interpretation of spectroscopic acidity data, intrinsic kinetics, and catalytic performance demonstrates that catalytic behavior arises from a balance between Brønsted site strength, effective site population, and confinement effects within the MFI framework. These findings provide a physically consistent basis for interpreting structure–acidity–activity relationships in Brønsted-acid-mediated reactions over microporous zeolites.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115804"},"PeriodicalIF":4.9,"publicationDate":"2026-03-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146186485","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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