Pub Date : 2026-02-15Epub Date: 2025-12-29DOI: 10.1016/j.mcat.2025.115682
Wen Liu , Qian Su , Zifeng Yang , Mengqian Fu , Yifan Liu , Weiguo Cheng
The conversion of CO₂ into cyclic carbonates is a feasible approach for CO2 mitigation. The environmentally friendly halide-free catalysts, which could avoid the waste halide contamination and industrial equipment corrosion are highly concerned. In this study, a series of halide-free ionic liquids with dual regulation of anion basicity and nucleophilicity were designed to achieve high catalytic efficiency. Among the synthesized ionic liquids, the [BmmIm][PA] demonstrated superior catalytic efficiency, delivering 94.9 % product yield with 99.9 % selectivity under the optimized conditions (70 °C, 2 mol%, 3.5 h, 10 bar). According to the deep activation energies analysis, the superior catalytic efficiency of [BmmIm][PA] was attributed to the strong nucleophilicity of [PA] reducing the ring-opening activation energy and the mild basicity of [PA] reducing the ring-closing activation energy simultaneously. The lower reaction activation energy catalyzed by [BmmIm][PA] was further confirmed by kinetic experiments. Finally, by combining DFT calculations with IR, NMR spectroscopy, a detailed catalytic mechanism involving direct epoxides activation by [PA], CO2 insertion and ring-closing was proposed. This work provided a more comprehensive understanding of halide-free catalysts and laid a theoretical foundation for the green and efficient conversion of CO2.
{"title":"Halide-free ionic liquids with dual-regulation of anion nucleophilicity and basicity for the efficient CO2 conversion into cyclic carbonates","authors":"Wen Liu , Qian Su , Zifeng Yang , Mengqian Fu , Yifan Liu , Weiguo Cheng","doi":"10.1016/j.mcat.2025.115682","DOIUrl":"10.1016/j.mcat.2025.115682","url":null,"abstract":"<div><div>The conversion of CO₂ into cyclic carbonates is a feasible approach for CO<sub>2</sub> mitigation. The environmentally friendly halide-free catalysts, which could avoid the waste halide contamination and industrial equipment corrosion are highly concerned. In this study, a series of halide-free ionic liquids with dual regulation of anion basicity and nucleophilicity were designed to achieve high catalytic efficiency. Among the synthesized ionic liquids, the [BmmIm][PA] demonstrated superior catalytic efficiency, delivering 94.9 % product yield with 99.9 % selectivity under the optimized conditions (70 °C, 2 mol%, 3.5 h, 10 bar). According to the deep activation energies analysis, the superior catalytic efficiency of [BmmIm][PA] was attributed to the strong nucleophilicity of [PA] reducing the ring-opening activation energy and the mild basicity of [PA] reducing the ring-closing activation energy simultaneously. The lower reaction activation energy catalyzed by [BmmIm][PA] was further confirmed by kinetic experiments. Finally, by combining DFT calculations with IR, NMR spectroscopy, a detailed catalytic mechanism involving direct epoxides activation by [PA], CO<sub>2</sub> insertion and ring-closing was proposed. This work provided a more comprehensive understanding of halide-free catalysts and laid a theoretical foundation for the green and efficient conversion of CO<sub>2</sub>.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115682"},"PeriodicalIF":4.9,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881759","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":"2026-02-15","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 : 2026-02-15Epub 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":"2026-02-15","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 : 2026-02-15Epub Date: 2026-01-10DOI: 10.1016/j.mcat.2026.115713
Ohud Almutairi , Amal Alasmari , Rawan Al-Faze , Elena F. Kozhevnikova , Ivan V. Kozhevnikov
Dehydration of 1-butanol primarily produces n-butene isomers, key olefinic feedstocks in the chemical industry. The reaction was studied in the gas phase using silica-supported Keggin heteropoly acids (HPAs) H3PW12O40 (HPW) and H4SiW12O40 (HSiW) as solid acid catalysts. The HPA catalysts were benchmarked against zeolites, such as H-ZSM-5, H-Mordenite and HY, the established catalysts for alcohol dehydration. The HPA catalysts were found to exhibit significantly higher activity and performance stability than zeolites. 25% HPW/SiO2 and 25% HSiW/SiO2 catalysts produced n-butene isomers at 130 °C with 99% selectivity (1-butene (8.4%) < cis-2-butene (30.3%) < trans-2-butene (61.3%)) at 99% conversion of 1-butanol and maintained stable performance for at least 24 h. The HPA-catalysed dehydration of 1-butanol followed the Langmuir rate equation, becoming zero-order in 1-butanol at partial pressures ≥1 kPa. A positive correlation between catalyst acid strength and reaction turnover rates was established. Evidence was provided that the reaction proceeds via a surface-type mechanism through an E2 elimination pathway.
{"title":"Silica-supported heteropoly acids as catalysts for low-temperature dehydration of 1-butanol in the gas phase: Application and mechanistic insight","authors":"Ohud Almutairi , Amal Alasmari , Rawan Al-Faze , Elena F. Kozhevnikova , Ivan V. Kozhevnikov","doi":"10.1016/j.mcat.2026.115713","DOIUrl":"10.1016/j.mcat.2026.115713","url":null,"abstract":"<div><div>Dehydration of 1-butanol primarily produces n-butene isomers, key olefinic feedstocks in the chemical industry. The reaction was studied in the gas phase using silica-supported Keggin heteropoly acids (HPAs) H<sub>3</sub>PW<sub>12</sub>O<sub>40</sub> (HPW) and H<sub>4</sub>SiW<sub>12</sub>O<sub>40</sub> (HSiW) as solid acid catalysts. The HPA catalysts were benchmarked against zeolites, such as H-ZSM-5, H-Mordenite and HY, the established catalysts for alcohol dehydration. The HPA catalysts were found to exhibit significantly higher activity and performance stability than zeolites. 25% HPW/SiO<sub>2</sub> and 25% HSiW/SiO<sub>2</sub> catalysts produced n-butene isomers at 130 °C with 99% selectivity (1-butene (8.4%) < cis-2-butene (30.3%) < trans-2-butene (61.3%)) at 99% conversion of 1-butanol and maintained stable performance for at least 24 h. The HPA-catalysed dehydration of 1-butanol followed the Langmuir rate equation, becoming zero-order in 1-butanol at partial pressures ≥1 kPa. A positive correlation between catalyst acid strength and reaction turnover rates was established. Evidence was provided that the reaction proceeds via a surface-type mechanism through an E2 elimination pathway.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115713"},"PeriodicalIF":4.9,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922433","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 : 2026-02-15Epub Date: 2025-12-31DOI: 10.1016/j.mcat.2025.115694
Yongfu Niu , Jianhua Guo , Xiaozhen Shi , Ming Su , Shujie Zhu , Guoyi Bai , Xin Wen
Hydrogenation of 1,3-dimethyl-5-nitroso-6-aminouracil (2Me-NAU) to 1,3-dimethyl-5,6-diaminouracil (2Me-DAU) is a pivotal step in xanthine drug synthesis. Residual acidic impurities from the preceding nitrosation step in dilute sulfuric acid severely deactivate conventional Raney nickel catalyst, causing rapid efficiency decay. To address this, for the first time, we developed an acid-resistant porous carbon-coated nickel phosphide catalyst (Ni2P@C) that effectively prevents Ni leaching during 2Me-NAU hydrogenation, superior to the Reney nickel catalyst. This catalyst achieves a remarkable 97.4 % 2Me-DAU yield under industrially relevant conditions. Comprehensive characterization confirms that an optimally thick carbon shell combined with controlled defect density maintains both high catalytic activity and exceptional stability (>18 cycles in pH 3.05 H2SO4), demonstrating its superior acid resistance as well as potential for large-scale application. This work provides a reference for designing acid-resistant non-noble metal catalysts and offers impetus for the green synthesis of xanthine drugs.
{"title":"Acid-resistant porous carbon shell coated nickel phosphide for the hydrogenation of xanthine intermediate","authors":"Yongfu Niu , Jianhua Guo , Xiaozhen Shi , Ming Su , Shujie Zhu , Guoyi Bai , Xin Wen","doi":"10.1016/j.mcat.2025.115694","DOIUrl":"10.1016/j.mcat.2025.115694","url":null,"abstract":"<div><div>Hydrogenation of 1,3-dimethyl-5-nitroso-6-aminouracil (2Me-NAU) to 1,3-dimethyl-5,6-diaminouracil (2Me-DAU) is a pivotal step in xanthine drug synthesis. Residual acidic impurities from the preceding nitrosation step in dilute sulfuric acid severely deactivate conventional Raney nickel catalyst, causing rapid efficiency decay. To address this, for the first time, we developed an acid-resistant porous carbon-coated nickel phosphide catalyst (Ni<sub>2</sub>P@C) that effectively prevents Ni leaching during 2Me-NAU hydrogenation, superior to the Reney nickel catalyst. This catalyst achieves a remarkable 97.4 % 2Me-DAU yield under industrially relevant conditions. Comprehensive characterization confirms that an optimally thick carbon shell combined with controlled defect density maintains both high catalytic activity and exceptional stability (>18 cycles in pH 3.05 H<sub>2</sub>SO<sub>4</sub>), demonstrating its superior acid resistance as well as potential for large-scale application. This work provides a reference for designing acid-resistant non-noble metal catalysts and offers impetus for the green synthesis of xanthine drugs.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115694"},"PeriodicalIF":4.9,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881757","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 : 2026-02-15Epub Date: 2025-12-20DOI: 10.1016/j.mcat.2025.115668
Payal Tyagi, Rajender Singh Malik
The CO2 cycloaddition with epoxides to form cyclic carbonate is environmentally benign and a 100 % atom-economic reaction for CO2 mitigation. A heterogeneous bifunctional nanomaterial, (1,1',1''-(1,3,5-triazine-2,4,6-triyl) tris(3-(3-(triethoxysilyl) propyl)-1H-imidazol-3-ium) chloride incorporated periodic mesoporous organosilica (PMO@TIT) was designed via a surfactant-templated co-condensation method. A series of PMO@TIT was prepared based on the molar ratio of TIT-organosilica precursor and tetraethyl orthosilicate (TEOS) [i.e., 1:10, 1:20 and 1:30] and structurally characterized. The obtained PMO@TIT have ordered mesoporous channels, high surface area, high structural stability and offered synergistic effect of hydrogen bond donor groups and quaternary ammonium moieties for CO2 adsorption and conversion under cycloaddition reaction. Moreover, the PMO@TIT samples exhibit appreciable CO₂ adsorption capacities, with uptake values reaching approximately 1000 mmol g⁻¹ at 273 K and ∼700 mmol g⁻¹ at 293 K (1 bar). These high capacities highlight the cooperative contribution of the highly accessible pore network, the enriched nitrogen-containing organic domains, and the embedded Lewis basic sites, collectively enabling efficient CO₂ capture and its subsequent transformation. The optimal combination of high surface area and multiple active sites made PMO@TIT-20 a more effective catalyst than the other two. It featured excellent catalytic activity having 98 % conversion with 96 % selectivity of chloropropene carbonate (CPC) at 5 bar pressure and 100 °C temperature within 8 h under solvent and co-catalyst-free conditions. 1H-NMR was used to analyse the catalytic activity of the catalyst. A 96 % conversion of epichlorohydrin with 90 % selectivity for chloropropene carbonate was observed even after five cycles, signifying its reusability. Moreover, PMO@TIT-20 exhibits exciting versatility, catalysing several epoxide conversions. Finally, a PMO@TIT-catalysed mechanism for cycloaddition reaction was proposed.
{"title":"Triazine–imidazole functionalized periodic Mesoporous Organosilica (PMO): A next-generation catalyst for CO₂ transformation","authors":"Payal Tyagi, Rajender Singh Malik","doi":"10.1016/j.mcat.2025.115668","DOIUrl":"10.1016/j.mcat.2025.115668","url":null,"abstract":"<div><div>The CO<sub>2</sub> cycloaddition with epoxides to form cyclic carbonate is environmentally benign and a 100 % atom-economic reaction for CO<sub>2</sub> mitigation. A heterogeneous bifunctional nanomaterial, (1,1',1''-(1,3,5-triazine-2,4,6-triyl) tris(3-(3-(triethoxysilyl) propyl)-1H-imidazol-3-ium) chloride incorporated periodic mesoporous organosilica (PMO@TIT) was designed via a surfactant-templated co-condensation method. A series of PMO@TIT was prepared based on the molar ratio of TIT-organosilica precursor and tetraethyl orthosilicate (TEOS) [i.e., 1:10, 1:20 and 1:30] and structurally characterized. The obtained PMO@TIT have ordered mesoporous channels, high surface area, high structural stability and offered synergistic effect of hydrogen bond donor groups and quaternary ammonium moieties for CO<sub>2</sub> adsorption and conversion under cycloaddition reaction. Moreover, the PMO@TIT samples exhibit appreciable CO₂ adsorption capacities, with uptake values reaching approximately 1000 mmol g⁻¹ at 273 K and ∼700 mmol g⁻¹ at 293 K (1 bar). These high capacities highlight the cooperative contribution of the highly accessible pore network, the enriched nitrogen-containing organic domains, and the embedded Lewis basic sites, collectively enabling efficient CO₂ capture and its subsequent transformation. The optimal combination of high surface area and multiple active sites made PMO@TIT-20 a more effective catalyst than the other two. It featured excellent catalytic activity having 98 % conversion with 96 % selectivity of chloropropene carbonate (CPC) at 5 bar pressure and 100 °C temperature within 8 h under solvent and co-catalyst-free conditions. <sup>1</sup>H-NMR was used to analyse the catalytic activity of the catalyst. A 96 % conversion of epichlorohydrin with 90 % selectivity for chloropropene carbonate was observed even after five cycles, signifying its reusability. Moreover, PMO@TIT-20 exhibits exciting versatility, catalysing several epoxide conversions. Finally, a PMO@TIT-catalysed mechanism for cycloaddition reaction was proposed.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115668"},"PeriodicalIF":4.9,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838959","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 : 2026-02-15Epub Date: 2025-12-30DOI: 10.1016/j.mcat.2025.115689
Wenyu Wang, Yaru Liu, Xiang Shao, Yuhao Zheng, Benyong Zhu, Jun Tang, Qiuhong Pan, Qingping Ke
The selective catalytic oxidation of biomass-derived compounds presents a considerable challenge due to the presence of multiple reactive sites. This study introduces a manganese-doped perovskite La0.5Sr0.5MnO3 (LSMn) photothermal catalyst, synthesized using a urea-redox & sol-gel process, to address this challenge. The as-synthesized LSMn catalyst demonstrates remarkable catalytic performance in the photothermal oxidative homo-coupling of isoeugenol to Licarin A under visible light (λ ≥ 420 nm) and mild temperature (75 °C). Under these conditions, the yield of Licarin A exceeds 90%, a substantial improvement relative with conventional thermal catalysis. Kinetics study reveals that the process operates as photothermal co-catalysis process. Mechanistic studies show that superoxide radicals (O2•−), generated through activation of O2 on the LSMn catalyst under visible light irradiation, and the chemisorption of isoeugenol on Mn3+ site under the mild temperature synergistically drive the reaction. These reactive intermediates (O2•−species and chemisorbed isoeugenol) facilitate the formation of isoeugenol-derived radicals, which undergo intramolecular conjugate addition and deprotonation to produce Licarin A, with H2O2 as a by-product. This study not only demonstrates the efficacy of the LSMn catalyst in the efficient activation and conversion of molecular oxygen (O2) but also provides critical insights into the design of sustainable, non-noble metal-based catalysts for the oxidative valorization of biomass-derived compounds.
{"title":"Lanthanide-based perovskites: Photothermal catalysts for highly yield synthesis of licarin a from oxidative homo-coupling of biomass-derived isoeugenol","authors":"Wenyu Wang, Yaru Liu, Xiang Shao, Yuhao Zheng, Benyong Zhu, Jun Tang, Qiuhong Pan, Qingping Ke","doi":"10.1016/j.mcat.2025.115689","DOIUrl":"10.1016/j.mcat.2025.115689","url":null,"abstract":"<div><div>The selective catalytic oxidation of biomass-derived compounds presents a considerable challenge due to the presence of multiple reactive sites. This study introduces a manganese-doped perovskite La<sub>0.5</sub>Sr<sub>0.5</sub>MnO<sub>3</sub> (LSMn) photothermal catalyst, synthesized using a urea-redox & sol-gel process, to address this challenge. The as-synthesized LSMn catalyst demonstrates remarkable catalytic performance in the photothermal oxidative homo-coupling of isoeugenol to Licarin A under visible light (λ ≥ 420 nm) and mild temperature (75 °C). Under these conditions, the yield of Licarin A exceeds 90%, a substantial improvement relative with conventional thermal catalysis. Kinetics study reveals that the process operates as photothermal co-catalysis process. Mechanistic studies show that superoxide radicals (O<sub>2</sub><sup>•−</sup>), generated through activation of O<sub>2</sub> on the LSMn catalyst under visible light irradiation, and the chemisorption of isoeugenol on Mn<sup>3+</sup> site under the mild temperature synergistically drive the reaction. These reactive intermediates (O<sub>2</sub><sup>•−</sup>species and chemisorbed isoeugenol) facilitate the formation of isoeugenol-derived radicals, which undergo intramolecular conjugate addition and deprotonation to produce Licarin A, with H<sub>2</sub>O<sub>2</sub> as a by-product. This study not only demonstrates the efficacy of the LSMn catalyst in the efficient activation and conversion of molecular oxygen (O<sub>2</sub>) but also provides critical insights into the design of sustainable, non-noble metal-based catalysts for the oxidative valorization of biomass-derived compounds.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115689"},"PeriodicalIF":4.9,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881754","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 : 2026-02-15Epub Date: 2025-12-31DOI: 10.1016/j.mcat.2025.115695
Shijun Huang , Yu Song , Shansi Zhong , Panpan Chang , Jinshi Dong , Jiaqiang Yang
Ni based catalysts are widely used in dry reforming of methane (DRM) but still face the issue of deactivation caused by sintering and carbon deposition. Pt doped Ni-Al2O3 catalyst was found of great durability which kept 100 % conversion of CO2 over 300 h without detectable loss in activity at 700 °C, while Ni-Al2O3 catalyst only maintained ∼10 h at the same condition. It is revealed that Pt and Ni are separately dispersed on Al2O3 with the structure of small Pt particles distributing around Ni like satellites. Kinetic experiments, temperature-programmed surface reactions (TPSR) and DFT calculations indicated that CH4 prefers to dissociatively adsorb on Pt surface but is hard to deeply crack to carbon because of the high energy barriers. As a result, the respective adsorption of CO2 on Ni and CHx on Pt surface largely reduced the bear of competitive adsorption and activation of both reactants on individual Ni and thus brought enhanced activity. Additionally, surrounding Pt effectively suppresses the sintering of Ni during reaction.
{"title":"Engineering the structure of satellitic Pt around Ni on Al2O3 to catalyze methane dry reforming with high durability","authors":"Shijun Huang , Yu Song , Shansi Zhong , Panpan Chang , Jinshi Dong , Jiaqiang Yang","doi":"10.1016/j.mcat.2025.115695","DOIUrl":"10.1016/j.mcat.2025.115695","url":null,"abstract":"<div><div>Ni based catalysts are widely used in dry reforming of methane (DRM) but still face the issue of deactivation caused by sintering and carbon deposition. Pt doped Ni-Al<sub>2</sub>O<sub>3</sub> catalyst was found of great durability which kept 100 % conversion of CO<sub>2</sub> over 300 h without detectable loss in activity at 700 °C, while Ni-Al<sub>2</sub>O<sub>3</sub> catalyst only maintained ∼10 h at the same condition. It is revealed that Pt and Ni are separately dispersed on Al<sub>2</sub>O<sub>3</sub> with the structure of small Pt particles distributing around Ni like satellites. Kinetic experiments, temperature-programmed surface reactions (TPSR) and DFT calculations indicated that CH<sub>4</sub> prefers to dissociatively adsorb on Pt surface but is hard to deeply crack to carbon because of the high energy barriers. As a result, the respective adsorption of CO<sub>2</sub> on Ni and CH<sub>x</sub> on Pt surface largely reduced the bear of competitive adsorption and activation of both reactants on individual Ni and thus brought enhanced activity. Additionally, surrounding Pt effectively suppresses the sintering of Ni during reaction.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115695"},"PeriodicalIF":4.9,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145881755","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}
This study introduces a novel type of carbon-doped amorphous titanium dioxide material FA-TiO2. It is synthesized through the modification of ferulic acid (FA), which facilitates the formation of more abundant oxygen vacancies in amorphous titanium dioxide, thereby enhancing its photocatalytic nitrogen fixation capabilities. It has been established through a range of characterization techniques that the FA modification exerts a substantial influence on the electronic structure, surface properties and photocatalytic activity of the catalyst. Compared with amorphous titanium dioxide, the nitrogen fixation efficiency of FA-TiO2 is as high as 155.19 µmol g⁻¹ h⁻¹, which is 11.14 times faster than TiO2. Additionally, the 15N2 isotope experiment qualitatively identified the nitrogen source employed in ammonia synthesis throughout the nitrogen fixation process involving FA-TiO2. The results indicate that the synergistic regulation of the electronic structure by doped carbon atoms is a simple method for preparing oxygen-vacancy photocatalysts, and the amorphous FA-TiO2 photocatalyst prepared has high efficient photocatalytic activity for nitrogen fixation.
{"title":"High effectively fixing nitrogen by Carbon-doped amorphous TiO2 with abundant oxygen vacancies under visible light and normal pressure and temperature","authors":"Jingyi Qu, Zhexiao Zhu, Jiahui Lin, Xiaolu Xu, Yangben Chen, Xintong Li, Runze Guo, Hui Zheng","doi":"10.1016/j.mcat.2026.115705","DOIUrl":"10.1016/j.mcat.2026.115705","url":null,"abstract":"<div><div>This study introduces a novel type of carbon-doped amorphous titanium dioxide material FA-TiO<sub>2</sub>. It is synthesized through the modification of ferulic acid (FA), which facilitates the formation of more abundant oxygen vacancies in amorphous titanium dioxide, thereby enhancing its photocatalytic nitrogen fixation capabilities. It has been established through a range of characterization techniques that the FA modification exerts a substantial influence on the electronic structure, surface properties and photocatalytic activity of the catalyst. Compared with amorphous titanium dioxide, the nitrogen fixation efficiency of FA-TiO<sub>2</sub> is as high as 155.19 µmol g⁻¹ h⁻¹, which is 11.14 times faster than TiO<sub>2</sub>. Additionally, the <sup>15</sup>N<sub>2</sub> isotope experiment qualitatively identified the nitrogen source employed in ammonia synthesis throughout the nitrogen fixation process involving FA-TiO<sub>2</sub>. The results indicate that the synergistic regulation of the electronic structure by doped carbon atoms is a simple method for preparing oxygen-vacancy photocatalysts, and the amorphous FA-TiO<sub>2</sub> photocatalyst prepared has high efficient photocatalytic activity for nitrogen fixation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115705"},"PeriodicalIF":4.9,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145922430","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 : 2026-02-15Epub Date: 2025-12-27DOI: 10.1016/j.mcat.2025.115688
Jiangkun Wang , Yuxi Tu , Yuan Yang , Xia Wang , Junsen Tong , Jianzhuang Yao
The escalating environmental burden of PET waste has prompted the pursuit of efficient enzymatic solutions for its degradation. This research successfully engineered the H218S/F222I variant based on a variant of the leaf and branch compost cutinase (ICCG), enhancing its PET hydrolysis capabilities through both computational and experimental studies. The variant demonstrated superior thermostability and catalytic efficiency, attributes crucial for industrial-scale PET recycling. Comprehensive kinetic analyses, utilizing both conventional and inverse Michaelis-Menten equations, underscored the variant's improved PET substrate affinity and reaction velocity. In particular, the reaction rate of ICCG-H218S/F222I are higher than that of ICCG across a range of temperatures (30–70 °C). Upon substrate normalization, the mutant delivered 96 % PET conversion within 24 h under high-loading conditions, substantially outperforming ICCG at 85 %, thus corroborating the engineered variant’s superior catalytic efficiency. Structural and QM/MM MD and free energy simulations studies elucidated the enzyme's reaction mechanisms, revealing temperature-dependent pathways that inform future enzyme optimizations. This work not only advances our understanding of PET hydrolases but also paves the way for developing more effective biocatalysts to combat plastic pollution.
{"title":"Biochemical characterization, crystal structure, and catalytic mechanism of a PET-hydrolase double mutant","authors":"Jiangkun Wang , Yuxi Tu , Yuan Yang , Xia Wang , Junsen Tong , Jianzhuang Yao","doi":"10.1016/j.mcat.2025.115688","DOIUrl":"10.1016/j.mcat.2025.115688","url":null,"abstract":"<div><div>The escalating environmental burden of PET waste has prompted the pursuit of efficient enzymatic solutions for its degradation. This research successfully engineered the H218S/F222I variant based on a variant of the leaf and branch compost cutinase (ICCG), enhancing its PET hydrolysis capabilities through both computational and experimental studies. The variant demonstrated superior thermostability and catalytic efficiency, attributes crucial for industrial-scale PET recycling. Comprehensive kinetic analyses, utilizing both conventional and inverse Michaelis-Menten equations, underscored the variant's improved PET substrate affinity and reaction velocity. In particular, the reaction rate of ICCG-H218S/F222I are higher than that of ICCG across a range of temperatures (30–70 °C). Upon substrate normalization, the mutant delivered 96 % PET conversion within 24 h under high-loading conditions, substantially outperforming ICCG at 85 %, thus corroborating the engineered variant’s superior catalytic efficiency. Structural and QM/MM MD and free energy simulations studies elucidated the enzyme's reaction mechanisms, revealing temperature-dependent pathways that inform future enzyme optimizations. This work not only advances our understanding of PET hydrolases but also paves the way for developing more effective biocatalysts to combat plastic pollution.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"591 ","pages":"Article 115688"},"PeriodicalIF":4.9,"publicationDate":"2026-02-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145838903","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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