Graphitic carbon nitride (g-C3N4) has emerged as a promising metal-free photocatalyst for solar driven hydrogen evolution. However, the rapid recombination of photogenerated electron-hole pairs in pristine g-C3N4 severely limits its opportunities for practical application. Herein, we developed an intramolecular S-scheme with an endogenous built-in electric field (BIEF) via simply ethylenediamine-mediated two-step thermal polycondensation, producing an heteroaromatic-modified g-C3N4 (HA-CN). The experimental results showed this structural innovation achieves dual optimization: (1) molecular-level integration of aromatic ring-modified melon (A-domain) and pristine melon-skeleton (P-domain) establish a BIEF to promote carriers transfer and separation; (2) the aromatic substitution extends π-electron delocalization of the adjacent melon domains, enhancing n→π* transitions and broadening visible-light absorption. The optimized HA-CN exhibited exceptional enhancement of hydrogen evolution (5.99 mmol g⁻¹ h⁻¹, λ ≥ 420 nm), surpassing pristine g-C3N4 by 39-fold, with an apparent quantum efficiency (AQE) of 3.93 % at 420 nm. Time-resolved spectroscopy and electrochemical analysis confirm the suppressed charge recombination and reduced interfacial charge-transfer resistance, corresponding to BIEF-driven directional carrier migration. This research offers valuable insights into junction engineering strategy from molecular level for designing efficient photocatalysts.
{"title":"Intramolecular S-scheme of g-C3N4 to boost photocatalytic hydrogen evolution","authors":"Ting He, Panting Song, Jinshu Wang, Junshu Wu, Jiawei Xiao, Yongli Li","doi":"10.1016/j.mcat.2026.115706","DOIUrl":"10.1016/j.mcat.2026.115706","url":null,"abstract":"<div><div>Graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>) has emerged as a promising metal-free photocatalyst for solar driven hydrogen evolution. However, the rapid recombination of photogenerated electron-hole pairs in pristine g-C<sub>3</sub>N<sub>4</sub> severely limits its opportunities for practical application. Herein, we developed an intramolecular S-scheme with an endogenous built-in electric field (BIEF) via simply ethylenediamine-mediated two-step thermal polycondensation, producing an heteroaromatic-modified g-C<sub>3</sub>N<sub>4</sub> (HA-CN). The experimental results showed this structural innovation achieves dual optimization: (1) molecular-level integration of aromatic ring-modified melon (A-domain) and pristine melon-skeleton (P-domain) establish a BIEF to promote carriers transfer and separation; (2) the aromatic substitution extends π-electron delocalization of the adjacent melon domains, enhancing n→π* transitions and broadening visible-light absorption. The optimized HA-CN exhibited exceptional enhancement of hydrogen evolution (5.99 mmol g⁻¹ h⁻¹, λ ≥ 420 nm), surpassing pristine g-C<sub>3</sub>N<sub>4</sub> by 39-fold, with an apparent quantum efficiency (AQE) of 3.93 % at 420 nm. Time-resolved spectroscopy and electrochemical analysis confirm the suppressed charge recombination and reduced interfacial charge-transfer resistance, corresponding to BIEF-driven directional carrier migration. This research offers valuable insights into junction engineering strategy from molecular level for designing efficient photocatalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115706"},"PeriodicalIF":4.9,"publicationDate":"2026-01-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922431","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 : 2026-01-08DOI: 10.1016/j.mcat.2026.115702
Yutong Wang , Chunyu Huang , Jelco Albertsma , Monique van der Veen , Miguel Alcalde , Frank Hollmann
Peroxide-dependent enzymes often suffer from irreversible oxidative deactivation by the peroxide co-substrate. Transition metal mediated in situ generation of H2O2 offers continuous peroxide feeding in low concentration. However, free metal complexes often interact non-selectively with proteins, leading to mutual deactivation of metal catalysts and enzymes. Here, we report a spatial isolation strategy using zirconium-based metal-organic frameworks (UiO-67) to immobilize the transition metal catalytic unit [Cp*Rh(bpy)Cl]⁺. The porous MOF structure acts as a molecular sieve, excluding enzymes from the Rh sites on the framework, thus protecting both catalysts from mutual deactivation. The Rh modified UiO-67 (Rh@UiO-67) catalyzes the flavin-mediated electron transfer from formate to oxygen, generating H2O2 in a formate oxidase mimicking fashion. Its protein compatibility allows Rh@UiO-67 to fuel peroxyzymes for stable oxyfunctionalization. Compared to natural formate oxidase, this system also shows high stability to various pH and temperatures, enabling its application in versatile conditions.
{"title":"MOF-constrained Rh enables stable in situ H2O2 supply for peroxide-dependent enzymes","authors":"Yutong Wang , Chunyu Huang , Jelco Albertsma , Monique van der Veen , Miguel Alcalde , Frank Hollmann","doi":"10.1016/j.mcat.2026.115702","DOIUrl":"10.1016/j.mcat.2026.115702","url":null,"abstract":"<div><div>Peroxide-dependent enzymes often suffer from irreversible oxidative deactivation by the peroxide co-substrate. Transition metal mediated in situ generation of H<sub>2</sub>O<sub>2</sub> offers continuous peroxide feeding in low concentration. However, free metal complexes often interact non-selectively with proteins, leading to mutual deactivation of metal catalysts and enzymes. Here, we report a spatial isolation strategy using zirconium-based metal-organic frameworks (UiO-67) to immobilize the transition metal catalytic unit [Cp*Rh(bpy)Cl]⁺. The porous MOF structure acts as a molecular sieve, excluding enzymes from the Rh sites on the framework, thus protecting both catalysts from mutual deactivation. The Rh modified UiO-67 (Rh@UiO-67) catalyzes the flavin-mediated electron transfer from formate to oxygen, generating H<sub>2</sub>O<sub>2</sub> in a formate oxidase mimicking fashion. Its protein compatibility allows Rh@UiO-67 to fuel peroxyzymes for stable oxyfunctionalization. Compared to natural formate oxidase, this system also shows high stability to various pH and temperatures, enabling its application in versatile conditions.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115702"},"PeriodicalIF":4.9,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922428","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}
Environmentally-friendly reutilization of sludge waste into active catalytic materials represents a promising strategy for sustainable waste management. Herein, solid acid catalysts were successfully prepared via a simple calcination process from the Fe- and Al-rich rubber sludge, with their acid strength strongly dependent on calcination temperature. Among them, the RS-400 catalyst, obtained at 400 °C, exhibited abundant acid sites and a well-developed porous structure by removing organic residues. Consequently, it delivered high catalytic activity for the catalytic transfer hydrogenation (CTH) of methyl levulinate (ML) to γ-valerolactone (GVL), achieving a 99% yield along with excellent recyclability and substrate universality. Isotopic labeling experiments further confirmed that the RS-400 catalyst drives the CTH reaction through the Meerwein-Ponndorf-Verley (MPV) mechanism. This work demonstrates a sustainable and cost-effective strategy for transforming industrial rubber sludge into efficient solid acid catalysts, providing new opportunities for waste valorization and green biomass conversion.
{"title":"From waste to wealth: Rubber sludge as a solid acid for the catalytic transfer hydrogenation of biomass-derived carbonyl compounds","authors":"Hua Li, Huai Liu, Rui Zhang, Wenlong Jia, Yongming Luo, Lincai Peng","doi":"10.1016/j.mcat.2026.115703","DOIUrl":"10.1016/j.mcat.2026.115703","url":null,"abstract":"<div><div>Environmentally-friendly reutilization of sludge waste into active catalytic materials represents a promising strategy for sustainable waste management. Herein, solid acid catalysts were successfully prepared via a simple calcination process from the Fe- and Al-rich rubber sludge, with their acid strength strongly dependent on calcination temperature. Among them, the RS-400 catalyst, obtained at 400 °C, exhibited abundant acid sites and a well-developed porous structure by removing organic residues. Consequently, it delivered high catalytic activity for the catalytic transfer hydrogenation (CTH) of methyl levulinate (ML) to γ-valerolactone (GVL), achieving a 99% yield along with excellent recyclability and substrate universality. Isotopic labeling experiments further confirmed that the RS-400 catalyst drives the CTH reaction through the Meerwein-Ponndorf-Verley (MPV) mechanism. This work demonstrates a sustainable and cost-effective strategy for transforming industrial rubber sludge into efficient solid acid catalysts, providing new opportunities for waste valorization and green biomass conversion.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115703"},"PeriodicalIF":4.9,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922426","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 : 2026-01-08DOI: 10.1016/j.mcat.2026.115707
Shuo Wan , Qing-Yuan Liu , Ting Lu , Yuan Jin , Rong-Sheng Zhai , Jian-Zhong Xu
Acetohydroxyacid synthase (AHAS) is a key rate-limiting enzyme in branched-chain amino acids (BCAAs) biosynthesis, yet its activity is inhibited by BCAAs, particularly L-valine. To overcome this limitation, we engineered a feedback-resistant AHAS variant to enhance L-valine production in Bacillus subtilis. To do this, an inducible mCherry-based whole-cell biosensor pVal for responding to L-valine was firstly constructed and was used to screen the L-valine high-producing strain B. subtilis Val-41.1 with IlvBL22E/A129V/A207S/A226G/V371P/S408T/K555EIlvHR3H/N29H/H37A/R45E/Q60L/G151D (i.e., IlvBMutIlvHMut), which produced 20.3 ± 1.9 g/L of L-valine in shake-flask fermentation. Subsequently, site-directed mutagenesis of wild-type IlvH was performed based on the IlvHR3H/N29H/H37A/R45E/Q60L/G151D, indicating that the variant IlvHG151D/N29H showed a higher degree of desensitization to L-valine than that of IlvHWT because it showed weaker interactions between L-valine and IlvH. In addition, overexpression of the IlvBMutIlvHG151D/N29H increased the final titer of L-valine in feed probiotics B. subtilis ACCC11025. The resulting strain ACCC11025/pMA5-ilvBMutilvHG151D/N29H produced 21.7 ± 1.8 g/L of L-valine, which was 90.4% higher than that of strain ACCC11025/pMA5-ilvBH with overexpression of the wild-type AHAS (i.e., IlvBWTIlvHWT). These findings provide a reference to construct a desensitizing IlvH variant with high enzyme activity and reconfirm that AHAS holoenzyme is a key enzyme for biosynthesizing L-valine.
{"title":"Evolution of acetohydroxyacid synthase from Bacillus subtilis for L-valine production using error-prone PCR","authors":"Shuo Wan , Qing-Yuan Liu , Ting Lu , Yuan Jin , Rong-Sheng Zhai , Jian-Zhong Xu","doi":"10.1016/j.mcat.2026.115707","DOIUrl":"10.1016/j.mcat.2026.115707","url":null,"abstract":"<div><div>Acetohydroxyacid synthase (AHAS) is a key rate-limiting enzyme in branched-chain amino acids (BCAAs) biosynthesis, yet its activity is inhibited by BCAAs, particularly L-valine. To overcome this limitation, we engineered a feedback-resistant AHAS variant to enhance L-valine production in <em>Bacillus subtilis</em>. To do this, an inducible mCherry-based whole-cell biosensor pVal for responding to L-valine was firstly constructed and was used to screen the L-valine high-producing strain <em>B. subtilis</em> Val-41.1 with IlvB<sup>L22E/A129V/A207S/A226G/V371P/S408T/K555E</sup>IlvH<sup>R3H/N29H/H37A/R45E/Q60L/G151D</sup> (i.e., IlvB<sup>Mut</sup>IlvH<sup>Mut</sup>), which produced 20.3 ± 1.9 g/L of L-valine in shake-flask fermentation. Subsequently, site-directed mutagenesis of wild-type IlvH was performed based on the IlvH<sup>R3H/N29H/H37A/R45E/Q60L/G151D</sup>, indicating that the variant IlvH<sup>G151D/N29H</sup> showed a higher degree of desensitization to L-valine than that of IlvH<sup>WT</sup> because it showed weaker interactions between L-valine and IlvH. In addition, overexpression of the IlvB<sup>Mut</sup>IlvH<sup>G151D/N29H</sup> increased the final titer of L-valine in feed probiotics <em>B. subtilis</em> ACCC11025. The resulting strain ACCC11025/pMA5-<em>ilvB</em><sup>Mut</sup><em>ilvH</em><sup>G151D/N29H</sup> produced 21.7 ± 1.8 g/L of L-valine, which was 90.4% higher than that of strain ACCC11025/pMA5-<em>ilvBH</em> with overexpression of the wild-type AHAS (i.e., IlvB<sup>WT</sup>IlvH<sup>WT</sup>). These findings provide a reference to construct a desensitizing IlvH variant with high enzyme activity and reconfirm that AHAS holoenzyme is a key enzyme for biosynthesizing L-valine.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115707"},"PeriodicalIF":4.9,"publicationDate":"2026-01-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922427","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 : 2026-01-07DOI: 10.1016/j.mcat.2025.115692
Kewei Zhang , Changjian Liao , Xinhong Han , Kuo Sun
Ethylene is a core raw material in the petrochemical industry. During the cracking production process, acetylene is inevitably produced, which seriously affects the subsequent polymerization. Consequently, the selective front-end hydrogenation catalytic removal of acetylene is imperative, and the efficacy of the catalyst is paramount in this regard. Herein, bimetallic NiM@C (M = Co, Cu, Fe, Mn, Zn) catalysts were synthesized by pyrolyzing metal-organic framework (MOF) precursors. During pyrolysis, the MOF framework undergoes thermal transformation, with organic ligands forming a uniform carbon layer that effectively safeguards the in-situ formed bimetallic active sites. The obtained alloy catalyst features a high specific surface area and a complete carbon layer, ensuring effective acetylene adsorption during the hydrogenation process while suppressing excessive ethylene adsorption. The formation of NiM alloy ensures the geometric isolation of Ni. Coupled with electronic synergy, this ensures excellent selectivity at high conversion rates. Additionally, the outer carbon layer retains the features of the original MOF, endowing the catalysts with excellent dispersion to facilitate rapid ethylene desorption post-reaction. Notably, NiZn@C exhibits the optimal conversion-selectivity balance: with the smallest nanoparticle size (6.1 nm) and strong electronic interaction, it achieves 95% acetylene conversion while maintaining 96% ethylene selectivity. It provides a certain theoretical basis and experimental evidence for the construction and design of high-performance acetylene selective hydrogenation catalysts.
{"title":"A MOF-precursor strategy to carbon-coated Ni-based bimetallic catalysts for the selective hydrogenation of acetylene","authors":"Kewei Zhang , Changjian Liao , Xinhong Han , Kuo Sun","doi":"10.1016/j.mcat.2025.115692","DOIUrl":"10.1016/j.mcat.2025.115692","url":null,"abstract":"<div><div>Ethylene is a core raw material in the petrochemical industry. During the cracking production process, acetylene is inevitably produced, which seriously affects the subsequent polymerization. Consequently, the selective front-end hydrogenation catalytic removal of acetylene is imperative, and the efficacy of the catalyst is paramount in this regard. Herein, bimetallic NiM@C (<em>M</em> = Co, Cu, Fe, Mn, Zn) catalysts were synthesized by pyrolyzing metal-organic framework (MOF) precursors. During pyrolysis, the MOF framework undergoes thermal transformation, with organic ligands forming a uniform carbon layer that effectively safeguards the in-situ formed bimetallic active sites. The obtained alloy catalyst features a high specific surface area and a complete carbon layer, ensuring effective acetylene adsorption during the hydrogenation process while suppressing excessive ethylene adsorption. The formation of NiM alloy ensures the geometric isolation of Ni. Coupled with electronic synergy, this ensures excellent selectivity at high conversion rates. Additionally, the outer carbon layer retains the features of the original MOF, endowing the catalysts with excellent dispersion to facilitate rapid ethylene desorption post-reaction. Notably, NiZn@C exhibits the optimal conversion-selectivity balance: with the smallest nanoparticle size (6.1 nm) and strong electronic interaction, it achieves 95% acetylene conversion while maintaining 96% ethylene selectivity. It provides a certain theoretical basis and experimental evidence for the construction and design of high-performance acetylene selective hydrogenation catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115692"},"PeriodicalIF":4.9,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922425","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 : 2026-01-07DOI: 10.1016/j.mcat.2025.115698
Feifei Yu , Shuwen Xue , Xia Xiang
Dual-atom catalysts (DACs) anchored on Janus MoSSe monolayers were systematically investigated for nitrogen reduction reaction (NRR) via density functional theory (DFT) calculations. Three heteronuclear DAC systems (Mo–Re, Mo–Os, and Re–Os) were constructed to explore synergistic effects induced by dual-metal coordination and substrate polarization. The chemically asymmetric Janus MoSSe substrate, featuring distinct sulfur (S) and selenium (Se) terminations, modulates charge redistribution at the catalytic centers, thereby facilitating nitrogen activation and intermediate stabilization. Among the studied systems, Mo–Re exhibits the most favorable overall catalytic performance, combining strong N₂ adsorption (ΔG = −1.00 eV), efficient electron transfer, and a relatively low reaction barrier (0.38 eV). In contrast, Mo–Os shows the strongest N₂ binding (ΔG = −1.40 eV) but suffers from a higher reaction barrier (1.61 eV), while Re–Os presents intermediate behavior with N₂ adsorption (ΔG = −1.32 eV) and reaction barrier (0.74 eV). The analysis of adsorption energetics, free energy profiles, and selectivity descriptors provides mechanistic insights into the structure–activity relationships of DACs on Janus supports. These results offer useful guidelines for the rational design of advanced atomically dispersed catalysts for sustainable ammonia synthesis.
{"title":"Dual-atom catalysts anchored on janus MoSSe monolayers for nitrogen reduction reaction: A DFT study of synergistic effects and selectivity","authors":"Feifei Yu , Shuwen Xue , Xia Xiang","doi":"10.1016/j.mcat.2025.115698","DOIUrl":"10.1016/j.mcat.2025.115698","url":null,"abstract":"<div><div>Dual-atom catalysts (DACs) anchored on Janus MoSSe monolayers were systematically investigated for nitrogen reduction reaction (NRR) via density functional theory (DFT) calculations. Three heteronuclear DAC systems (Mo–<em>Re</em>, Mo–Os, and <em>Re</em>–Os) were constructed to explore synergistic effects induced by dual-metal coordination and substrate polarization. The chemically asymmetric Janus MoSSe substrate, featuring distinct sulfur (S) and selenium (Se) terminations, modulates charge redistribution at the catalytic centers, thereby facilitating nitrogen activation and intermediate stabilization. Among the studied systems, Mo–<em>Re</em> exhibits the most favorable overall catalytic performance, combining strong N₂ adsorption (ΔG = −1.00 eV), efficient electron transfer, and a relatively low reaction barrier (0.38 eV). In contrast, Mo–Os shows the strongest N₂ binding (ΔG = −1.40 eV) but suffers from a higher reaction barrier (1.61 eV), while <em>Re</em>–Os presents intermediate behavior with N₂ adsorption (ΔG = −1.32 eV) and reaction barrier (0.74 eV). The analysis of adsorption energetics, free energy profiles, and selectivity descriptors provides mechanistic insights into the structure–activity relationships of DACs on Janus supports. These results offer useful guidelines for the rational design of advanced atomically dispersed catalysts for sustainable ammonia synthesis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115698"},"PeriodicalIF":4.9,"publicationDate":"2026-01-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922424","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 : 2026-01-06DOI: 10.1016/j.mcat.2026.115701
Kuan Wang , Yue Yang , Xin-Peng Li , Zhe Cao , Mei-Jie Shi , Zhen-Hong He , Yi-Fan Tang , Wen-Shuo Li , Weitao Wang , Huan Wang , Hui Ma , Zhao-Tie Liu
Trifluoromethyl functional group (-CF3) plays a significant role in the synthesis of fluorinated compounds due to its unique electronic effect and strong lipophilicity. However, the existing heterogeneous catalyst systems are subject to certain limitations in the trifluoromethylation process, including low catalytic efficiency, harsh reaction conditions, and the requirement of strong acids or bases. Herein, an ultrathin ZnO/NaVO3 composite catalyst featuring strong Lewis acidic sites was rationally designed and synthesized to catalyze the trifluoromethylation of acetophenone, enabling the highly efficient selective synthesis of 1,1,1-trifluoro-2-phenylpropan-2-ol. Notably, the activation of ultrathin ZnO/NaVO3 surface assisted by strong Lewis acidic sites effectively enhanced the trifluoromethylation reaction, achieving a 97 % yield of 1,1,1-trifluoro-2-phenylpropan-2-ol. The reaction kinetics and mechanistic pathways were systematically examined to elucidate the role of Lewis acid sites in enhancing trifluoromethylation. Furthermore, the catalytic system does not require the use of strong acid or base, and its preparation method is straightforward and environmentally benign, which is conducive to the sustainability of resources as well as industrial production. The present study unveils a new design paradigm for ultrathin homogeneous catalysts whose surface Lewis acid sites drive trifluoromethylation reactions with exceptional efficiency.
{"title":"Strong Lewis acidic sites assisted ultrathin ZnO/NaVO3 surface activation for efficient nucleophilic trifluoromethylation of ketones","authors":"Kuan Wang , Yue Yang , Xin-Peng Li , Zhe Cao , Mei-Jie Shi , Zhen-Hong He , Yi-Fan Tang , Wen-Shuo Li , Weitao Wang , Huan Wang , Hui Ma , Zhao-Tie Liu","doi":"10.1016/j.mcat.2026.115701","DOIUrl":"10.1016/j.mcat.2026.115701","url":null,"abstract":"<div><div>Trifluoromethyl functional group (-CF<sub>3</sub>) plays a significant role in the synthesis of fluorinated compounds due to its unique electronic effect and strong lipophilicity. However, the existing heterogeneous catalyst systems are subject to certain limitations in the trifluoromethylation process, including low catalytic efficiency, harsh reaction conditions, and the requirement of strong acids or bases. Herein, an ultrathin ZnO/NaVO<sub>3</sub> composite catalyst featuring strong Lewis acidic sites was rationally designed and synthesized to catalyze the trifluoromethylation of acetophenone, enabling the highly efficient selective synthesis of 1,1,1-trifluoro-2-phenylpropan-2-ol. Notably, the activation of ultrathin ZnO/NaVO<sub>3</sub> surface assisted by strong Lewis acidic sites effectively enhanced the trifluoromethylation reaction, achieving a 97 % yield of 1,1,1-trifluoro-2-phenylpropan-2-ol. The reaction kinetics and mechanistic pathways were systematically examined to elucidate the role of Lewis acid sites in enhancing trifluoromethylation. Furthermore, the catalytic system does not require the use of strong acid or base, and its preparation method is straightforward and environmentally benign, which is conducive to the sustainability of resources as well as industrial production. The present study unveils a new design paradigm for ultrathin homogeneous catalysts whose surface Lewis acid sites drive trifluoromethylation reactions with exceptional efficiency.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115701"},"PeriodicalIF":4.9,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922423","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}
Direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol is thermodynamically challenging and requires catalysts with finely tuned surface properties. In this work, we present the design and synthesis of a series of nitrogen- and sulfur-assisted, defect-modulated ceria nanorods (NXCeO2-NR and SXCeO2-NR) to tailor oxygen vacancy density, Ce3+ concentration, surface acidity, and basicity, to assess their catalytic performance in DMC synthesis. The nanomaterials were comprehensively characterized by Raman spectroscopy, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM), Brunauer–Emmett–Teller (BET) surface analysis, and temperature-programmed desorption (TPD) of CO2 and NH3. Compared to pristine nanorod CeO2 (CeO2-NR) and nanopolyhedron CeO2 (CeO2-NP), the defect-modulated materials displayed markedly enhanced catalytic activity. Specifically, N6CeO2-NR and S6CeO2-NR achieved the highest DMC productivity of 66.4 and 63.3 mmol , respectively, with nearly 100% selectivity under moderate reaction conditions in the presence of a dehydrating reagent 2-cyanopyridine (2-CP). The remarkable performance of N6CeO2-NR and S6CeO2-NR can be attributed to their significantly improved surface properties, including balanced acidity, basicity, elevated Ce3+ ion concentration, and increased oxygen vacancy density. These enhancements, which distinguish them from the pristine CeO2, were confirmed through detailed analyses using TPD, XPS, and Raman spectroscopy. These findings highlight N- and S-assisted defect-engineered CeO2 nanomaterials as a promising class of catalysts for DMC synthesis.
{"title":"Promoting CO2 conversion to dimethyl carbonate with N- and S-assisted defect-modulated CeO2 nanomaterials","authors":"Niladri Maity , Norah Al-Fayez , Samiyah A. Al-Jendan , E.A. Jaseer , Nagendra Kulal","doi":"10.1016/j.mcat.2025.115696","DOIUrl":"10.1016/j.mcat.2025.115696","url":null,"abstract":"<div><div>Direct synthesis of dimethyl carbonate (DMC) from CO<sub>2</sub> and methanol is thermodynamically challenging and requires catalysts with finely tuned surface properties. In this work, we present the design and synthesis of a series of nitrogen- and sulfur-assisted, defect-modulated ceria nanorods (N<sub>X</sub>CeO<sub>2</sub>-NR and S<sub>X</sub>CeO<sub>2</sub>-NR) to tailor oxygen vacancy density, Ce<sup>3+</sup> concentration, surface acidity, and basicity, to assess their catalytic performance in DMC synthesis. The nanomaterials were comprehensively characterized by Raman spectroscopy, powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), high-resolution transmission electron microscopy (HR-TEM), Brunauer–Emmett–Teller (BET) surface analysis, and temperature-programmed desorption (TPD) of CO<sub>2</sub> and NH<sub>3</sub>. Compared to pristine nanorod CeO<sub>2</sub> (CeO<sub>2</sub>-NR) and nanopolyhedron CeO<sub>2</sub> (CeO<sub>2</sub>-NP), the defect-modulated materials displayed markedly enhanced catalytic activity. Specifically, N<sub>6</sub>CeO<sub>2</sub>-NR and S<sub>6</sub>CeO<sub>2</sub>-NR achieved the highest DMC productivity of 66.4 and 63.3 mmol <span><math><mrow><msubsup><mi>g</mi><mrow><mtext>cat</mtext></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msubsup><mspace></mspace><msup><mrow><mi>h</mi></mrow><mrow><mo>−</mo><mn>1</mn></mrow></msup></mrow></math></span>, respectively, with nearly 100% selectivity under moderate reaction conditions in the presence of a dehydrating reagent 2-cyanopyridine (2-CP). The remarkable performance of N<sub>6</sub>CeO<sub>2</sub>-NR and S<sub>6</sub>CeO<sub>2</sub>-NR can be attributed to their significantly improved surface properties, including balanced acidity, basicity, elevated Ce<sup>3+</sup> ion concentration, and increased oxygen vacancy density. These enhancements, which distinguish them from the pristine CeO<sub>2</sub>, were confirmed through detailed analyses using TPD, XPS, and Raman spectroscopy. These findings highlight N- and S-assisted defect-engineered CeO<sub>2</sub> nanomaterials as a promising class of catalysts for DMC synthesis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115696"},"PeriodicalIF":4.9,"publicationDate":"2026-01-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921910","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 sustainable design of heterogeneous catalysts that simultaneously capture and convert CO2 remains a central challenge in green chemistry. Herein, we report a facile and eco-friendly strategy for the aqueous encapsulation of cobalt(III)-substituted Keggin-type heteropolytungstate (K5[CoW12O40], Co-HPW) into the mesoporous MIL-100(Fe) framework at 60 °C under ambient pressure, avoiding the need for autoclaves or high-temperature hydrothermal synthesis. The resulting hybrid, Co-HPW@MIL-100(Fe), was thoroughly characterized by PXRD, FTIR, BET, SEM, TEM, TGA, and ICP, confirming structural integrity and successful polyoxometalate (POM) incorporation. Benefiting from the synergistic interplay between the redox-active Co-HPW and the CO2-adsorptive MIL-100(Fe) matrix, the composite catalyst exhibited high catalytic activity for the solvent-free cycloaddition of CO2 with epoxides. Under optimized conditions, conversions of 86–92% and selectivities of up to 92% were achieved across a broad substrate scope, with a notable turnover frequency of 1380 h−1 for epichlorohydrin. Moreover, Co-HPW@MIL-100(Fe) retained over 83% of its catalytic efficiency after five consecutive runs with negligible Co-HPW leaching (<2%). This scalable, recyclable, and highly efficient POM@MOF platform offers a promising route for sustainable CO2 valorization via green catalytic processes.
{"title":"Sustainable CO2 valorization via solvent-free cycloaddition over Co(III)-substituted Keggin-type heteropolytungstate encapsulated in iron-based MIL-100","authors":"Sadegh Safaei, Mahan Mirzaeian, Afsaneh Marandi, Shahram Tangestaninejad, Majid Moghadam, Iraj Mohammadpoor-Baltork","doi":"10.1016/j.mcat.2025.115700","DOIUrl":"10.1016/j.mcat.2025.115700","url":null,"abstract":"<div><div>The sustainable design of heterogeneous catalysts that simultaneously capture and convert CO<sub>2</sub> remains a central challenge in green chemistry. Herein, we report a facile and eco-friendly strategy for the aqueous encapsulation of cobalt(III)-substituted Keggin-type heteropolytungstate (K<sub>5</sub>[CoW<sub>12</sub>O<sub>40</sub>], Co-HPW) into the mesoporous MIL-100(Fe) framework at 60 °C under ambient pressure, avoiding the need for autoclaves or high-temperature hydrothermal synthesis. The resulting hybrid, Co-HPW@MIL-100(Fe), was thoroughly characterized by PXRD, FTIR, BET, SEM, TEM, TGA, and ICP, confirming structural integrity and successful polyoxometalate (POM) incorporation. Benefiting from the synergistic interplay between the redox-active Co-HPW and the CO<sub>2</sub>-adsorptive MIL-100(Fe) matrix, the composite catalyst exhibited high catalytic activity for the solvent-free cycloaddition of CO<sub>2</sub> with epoxides. Under optimized conditions, conversions of 86–92% and selectivities of up to 92% were achieved across a broad substrate scope, with a notable turnover frequency of 1380 h<sup>−1</sup> for epichlorohydrin. Moreover, Co-HPW@MIL-100(Fe) retained over 83% of its catalytic efficiency after five consecutive runs with negligible Co-HPW leaching (<2%). This scalable, recyclable, and highly efficient POM@MOF platform offers a promising route for sustainable CO<sub>2</sub> valorization via green catalytic processes.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115700"},"PeriodicalIF":4.9,"publicationDate":"2026-01-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145921909","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 : 2026-01-03DOI: 10.1016/j.mcat.2025.115699
Donghui Zhang , Xinyue Mo , Jingwei Liu , Lingyan Wang , Jingxiang Zhao
Nitrate degradation and ammonia production are of great significance for both agriculture and industry. In this work, we designed three types of two-dimensional metalloporphyrin frameworks (M-Pp, M-Pp0, and M-Pp45, M = 3d ∼ 5d) and studied their catalytic performances of nitrate reduction reaction (NO3RR) by density functional theory. The computational results demonstrate that three Ti-based metalloporphyrin frameworks are optimal electrocatalysts for NO3RR due to the favorable limiting potential (-0.26, -0.22, and -0.29 V), high selectivity toward NH3, as well as superior thermodynamic and electrochemical stabilities, which guarantee their practical applicability in NO3RR. The excellent catalytic activities of the three Ti-based metalloporphyrin frameworks are attributed to their moderate electronic properties as well as the local structure and chemical environment of the Ti active site. Our study not only investigates the NO3RR catalytic potential of metalloporphyrin frameworks, but also provides a novel route for the rational design of high-performance and stable electrocatalysts.
硝酸盐的降解和制氨对农业和工业都有重要意义。本文设计了三种二维金属卟啉框架（M- pp、M- pp0和M- pp45， M = 3d ~ 5d），并利用密度泛函理论研究了它们在硝酸还原反应（NO3RR）中的催化性能。计算结果表明，三种钛基金属卟啉框架具有良好的极限电位（-0.26、-0.22和-0.29 V），对NH3的选择性高，以及优异的热力学和电化学稳定性，是NO3RR的最佳电催化剂，保证了它们在NO3RR中的实际适用性。三种钛基金属卟啉框架具有优异的催化活性，主要归因于其温和的电子性质以及钛活性位点的局部结构和化学环境。本研究不仅考察了金属卟啉框架的NO3RR催化潜能，也为合理设计高性能、稳定的电催化剂提供了新的途径。
{"title":"Theoretical study on two-dimensional metalloporphyrin monolayers as promising single-atom-catalysts for nitrate electroreduction to ammonia","authors":"Donghui Zhang , Xinyue Mo , Jingwei Liu , Lingyan Wang , Jingxiang Zhao","doi":"10.1016/j.mcat.2025.115699","DOIUrl":"10.1016/j.mcat.2025.115699","url":null,"abstract":"<div><div>Nitrate degradation and ammonia production are of great significance for both agriculture and industry. In this work, we designed three types of two-dimensional metalloporphyrin frameworks (M-Pp, M-Pp0, and M-Pp45, <em>M</em> = 3d ∼ 5d) and studied their catalytic performances of nitrate reduction reaction (NO<sub>3</sub>RR) by density functional theory. The computational results demonstrate that three Ti-based metalloporphyrin frameworks are optimal electrocatalysts for NO<sub>3</sub>RR due to the favorable limiting potential (-0.26, -0.22, and -0.29 V), high selectivity toward NH<sub>3</sub>, as well as superior thermodynamic and electrochemical stabilities, which guarantee their practical applicability in NO<sub>3</sub>RR. The excellent catalytic activities of the three Ti-based metalloporphyrin frameworks are attributed to their moderate electronic properties as well as the local structure and chemical environment of the Ti active site. Our study not only investigates the NO<sub>3</sub>RR catalytic potential of metalloporphyrin frameworks, but also provides a novel route for the rational design of high-performance and stable electrocatalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115699"},"PeriodicalIF":4.9,"publicationDate":"2026-01-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881376","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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