Titanium-containing materials with different Mg:Ti:Al molar ratios and phase compositions, were obtained by coprecipitation with subsequent hydrothermal treatment. A sequential increase in the molar fraction of titanium in the reaction mixture leads to the formation of anatase instead of the hydrotalcite structure, and a change in the ratio of Ti4+ in a tetrahedral or octahedral coordination. An extreme dependence of the conversion of styrene, selectivity and yield of 4-phenyl-1,3-dioxolan-2-one in cycloaddition reaction on the molar content of titanium was established, and it was shown that the maximum catalytic performance (yield of the desired cyclic carbonate up to 100 %) are achieved for the sample prepared from the reaction mixtures with the Mg:Ti:Al ratio of 2:1.5:1.
{"title":"Exceptional selectivity of Ti-containing hydrotalcites in tandem transformation of styrene and carbon dioxide into cyclic carbonates","authors":"Natalia Romanovska, Mykhailo Kurmach, Pavlo Yaremov, Valentyna Tsyrina, Oleksiy Shvets, Petro Manoryk","doi":"10.1016/j.mcat.2025.115659","DOIUrl":"10.1016/j.mcat.2025.115659","url":null,"abstract":"<div><div>Titanium-containing materials with different Mg:Ti:Al molar ratios and phase compositions, were obtained by coprecipitation with subsequent hydrothermal treatment. A sequential increase in the molar fraction of titanium in the reaction mixture leads to the formation of anatase instead of the hydrotalcite structure, and a change in the ratio of Ti4+ in a tetrahedral or octahedral coordination. An extreme dependence of the conversion of styrene, selectivity and yield of 4-phenyl-1,3-dioxolan-2-one in cycloaddition reaction on the molar content of titanium was established, and it was shown that the maximum catalytic performance (yield of the desired cyclic carbonate up to 100 %) are achieved for the sample prepared from the reaction mixtures with the Mg:Ti:Al ratio of 2:1.5:1.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115659"},"PeriodicalIF":4.9,"publicationDate":"2025-12-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145787318","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 : 2025-12-12DOI: 10.1016/j.mcat.2025.115663
Hong Wang , Peiyong Wang , Minghui Du , Ruohan Wang , Binzhi Zhang , Wei Li , Shuichen Yan , Biao Wu , Jianxin Li
Sodium 2,2,3,3-tetrafluoropropionate (STFP) is a key fluorochemical, but conventional synthesis faces harsh conditions and pollution. Herein, an electrochemical membrane reactor (ECMR) was developed for the green synthesis of STFP. MnOx/Ti membrane anodes with varying MnOx loadings were prepared via ultrasonic-assisted impregnation-pyrolysis. In the ECMR (MnOx/Ti anode, stainless-steel mesh cathode), a mixed aqueous solution of 2,2,3,3-tetrafluoro-1-propanol (TFP) and NaOH was oxidized to yield STFP permeate. Electron spin resonance and radical quenching elucidated the mechanism. Under the optimized conditions, the 6.58 wt% MnOx/Ti electrode exhibited optimal activity due to uniform MnOx dispersion, achieving 34.68 % TFP conversion and 94.02 % STFP selectivity. Efficient synthesis is attributed to a synergistic mechanism: direct electron transfer mediated by Mn(IV) and anodic hole-induced •OH radical generation. Specifically, the three-dimensional porous structure of the MnOx/Ti membrane electrode enhanced mass transfer and promoted the contact between TFP and •OH/Mn(IV) active sites, finally accelerating product efflux, thereby improving reaction efficiency and selectivity. Purification of ECMR permeate yielded STFP with 90.27 % purity. This work provides a green strategy for sustainable fluorochemical synthesis.
{"title":"Synergistic dual-path electrosynthesis of sodium 2,2,3,3-tetrafluoropropionate enabled by microporous confinement in electrocatalytic membrane reactor","authors":"Hong Wang , Peiyong Wang , Minghui Du , Ruohan Wang , Binzhi Zhang , Wei Li , Shuichen Yan , Biao Wu , Jianxin Li","doi":"10.1016/j.mcat.2025.115663","DOIUrl":"10.1016/j.mcat.2025.115663","url":null,"abstract":"<div><div>Sodium 2,2,3,3-tetrafluoropropionate (STFP) is a key fluorochemical, but conventional synthesis faces harsh conditions and pollution. Herein, an electrochemical membrane reactor (ECMR) was developed for the green synthesis of STFP. MnO<sub>x</sub>/Ti membrane anodes with varying MnO<sub>x</sub> loadings were prepared via ultrasonic-assisted impregnation-pyrolysis. In the ECMR (MnO<sub>x</sub>/Ti anode, stainless-steel mesh cathode), a mixed aqueous solution of 2,2,3,3-tetrafluoro-1-propanol (TFP) and NaOH was oxidized to yield STFP permeate. Electron spin resonance and radical quenching elucidated the mechanism. Under the optimized conditions, the 6.58 wt% MnO<sub>x</sub>/Ti electrode exhibited optimal activity due to uniform MnO<sub>x</sub> dispersion, achieving 34.68 % TFP conversion and 94.02 % STFP selectivity. Efficient synthesis is attributed to a synergistic mechanism: direct electron transfer mediated by Mn(IV) and anodic hole-induced •OH radical generation. Specifically, the three-dimensional porous structure of the MnO<sub>x</sub>/Ti membrane electrode enhanced mass transfer and promoted the contact between TFP and •OH/Mn(IV) active sites, finally accelerating product efflux, thereby improving reaction efficiency and selectivity. Purification of ECMR permeate yielded STFP with 90.27 % purity. This work provides a green strategy for sustainable fluorochemical synthesis.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115663"},"PeriodicalIF":4.9,"publicationDate":"2025-12-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734050","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}
A series of gold-decorated titanium dioxide (Aux/HT) photocatalysts was synthesized by a sequential hydrothermal and photodeposition for the photocatalytic reforming of glycerol solution to green hydrogen (H2). The presence of metallic Au in the range of 0.25 to 1.50 wt. % had an insignificant effect on the TiO2 crystallite size, phase composition, porosity, and bandgap values compared to the pristine HT. However, the Au decoration significantly enhanced the visible light response, suppressed the charge recombination, and promoted the charge carrier migration. Among all explored photocatalysts, the Au0.75/HT exhibited the highest photocatalytic H2 production, attributing to its high BET surface area and optimal hemispherical surface structure. Apart the glycerol concentration and photocatalyst loading, types of glycerol feedstocks had a significant impact on the H2 production. Among all the evaluated glycerol types, the refined crude glycerol achieved the highest H2 output at 15 vol. % glycerol concentration and a photocatalyst loading of 3.0 g/L. This resulted in an H2 production rate of 216.2 µmol/g·h (or 387.6 µmol after 3 h), approximately 1.22 and 1.59 times higher than those from commercial- and crude glycerol, respectively. Additionally, it demonstrated an outstanding long-term H2 production and cost-effectiveness ($8.3 /mmol), which was comparable to that of commercial glycerol and approximately 3.41 times cheaper than that of crude glycerol.
{"title":"Mechanistic insights into photocatalytic hydrogen evolution from crude glycerol solution over gold-decorated TiO2 nanostructures","authors":"Thanapol Sutthiphong , Auttawit Thoumrungroj , Pimchanok Longchin , Mali Hunsom","doi":"10.1016/j.mcat.2025.115657","DOIUrl":"10.1016/j.mcat.2025.115657","url":null,"abstract":"<div><div>A series of gold-decorated titanium dioxide (Au<em><sub>x</sub></em>/HT) photocatalysts was synthesized by a sequential hydrothermal and photodeposition for the photocatalytic reforming of glycerol solution to green hydrogen (H<sub>2</sub>). The presence of metallic Au in the range of 0.25 to 1.50 wt. % had an insignificant effect on the TiO<sub>2</sub> crystallite size, phase composition, porosity, and bandgap values compared to the pristine HT. However, the Au decoration significantly enhanced the visible light response, suppressed the charge recombination, and promoted the charge carrier migration. Among all explored photocatalysts, the Au<sub>0.75</sub>/HT exhibited the highest photocatalytic H<sub>2</sub> production, attributing to its high BET surface area and optimal hemispherical surface structure. Apart the glycerol concentration and photocatalyst loading, types of glycerol feedstocks had a significant impact on the H<sub>2</sub> production. Among all the evaluated glycerol types, the refined crude glycerol achieved the highest H<sub>2</sub> output at 15 vol. % glycerol concentration and a photocatalyst loading of 3.0 g/L. This resulted in an H<sub>2</sub> production rate of 216.2 µmol/g·h (or 387.6 µmol after 3 h), approximately 1.22 and 1.59 times higher than those from commercial- and crude glycerol, respectively. Additionally, it demonstrated an outstanding long-term H<sub>2</sub> production and cost-effectiveness ($8.3 /mmol), which was comparable to that of commercial glycerol and approximately 3.41 times cheaper than that of crude glycerol.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115657"},"PeriodicalIF":4.9,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734054","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 : 2025-12-10DOI: 10.1016/j.mcat.2025.115655
Zhenping Su , Min Liu , Dongping Wang , Shengming Lu , Jun Li
Nowadays, bifunctional catalysts have attracted considerable attention for their superior catalytic efficiency in the cycloaddition reactions of CO2 to produce corresponding cyclic carbonates. Herein, three bifunctional zinc porphyrin-based organic polymers Poly(ZnTAEImP/BDDA), Poly(ZnTAEImP/PPA) and Poly(ZnTAEImP/PD) were synthesized successfully through the free-radical copolymerization of a novel bifunctional zinc porphyrin ZnTAEImP with three structurally similar flexible linker monomers, 1,4-butanediol diacrylate (BDDA), phenyl ethylene glycol diacrylate (PPA), and 1,4-phenylene diacrylate (PD), respectively. A comprehensive series of characterizations were subsequently performed to verify the structural integrity and properties of the prepared polymers. All three polymers possessed well-defined bifunctional active sites, including Zn²⁺ Lewis acid centers and Br⁻ nucleophilic species. Among them, the Poly(ZnTAEImP/PD) demonstrated exceptional solvent-responsive swelling capacity and robust thermal stability. Notably, Poly(ZnTAEImP/PD) exhibited superior catalytic performance in the cycloaddition reaction between CO₂ and epichlorohydrin (ECH), achieving 99% cyclic carbonate yield under optimized conditions (1.0 MPa CO₂, 120 °C, 12 h). Additionally, Poly(ZnTAEImP/PD) also displayed broad substrate universality and excellent cycling stability, indicating promising application prospects.
{"title":"Bifunctional zinc porphyrin-based organic polymers with peripheral flexible linkers as efficient catalysts for CO2 cycloaddition reactions","authors":"Zhenping Su , Min Liu , Dongping Wang , Shengming Lu , Jun Li","doi":"10.1016/j.mcat.2025.115655","DOIUrl":"10.1016/j.mcat.2025.115655","url":null,"abstract":"<div><div>Nowadays, bifunctional catalysts have attracted considerable attention for their superior catalytic efficiency in the cycloaddition reactions of CO<sub>2</sub> to produce corresponding cyclic carbonates. Herein, three bifunctional zinc porphyrin-based organic polymers Poly(ZnTAEImP/BDDA), Poly(ZnTAEImP/PPA) and Poly(ZnTAEImP/PD) were synthesized successfully through the free-radical copolymerization of a novel bifunctional zinc porphyrin ZnTAEImP with three structurally similar flexible linker monomers, 1,4-butanediol diacrylate (BDDA), phenyl ethylene glycol diacrylate (PPA), and 1,4-phenylene diacrylate (PD), respectively. A comprehensive series of characterizations were subsequently performed to verify the structural integrity and properties of the prepared polymers. All three polymers possessed well-defined bifunctional active sites, including Zn²⁺ Lewis acid centers and Br⁻ nucleophilic species. Among them, the Poly(ZnTAEImP/PD) demonstrated exceptional solvent-responsive swelling capacity and robust thermal stability. Notably, Poly(ZnTAEImP/PD) exhibited superior catalytic performance in the cycloaddition reaction between CO₂ and epichlorohydrin (ECH), achieving 99% cyclic carbonate yield under optimized conditions (1.0 MPa CO₂, 120 °C, 12 h). Additionally, Poly(ZnTAEImP/PD) also displayed broad substrate universality and excellent cycling stability, indicating promising application prospects.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115655"},"PeriodicalIF":4.9,"publicationDate":"2025-12-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734055","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 : 2025-12-09DOI: 10.1016/j.mcat.2025.115656
Christos Lykos , Charalampos Drivas , Mark A. Isaacs , Kalliopi Ladomenou , George Z. Kyzas , Triantafyllos Albanis , Ioannis Konstantinou
Tungsten trioxide (WO₃) is an n-type semiconductor with a relatively narrow band gap, which enables its photoactivation under visible light. However, its application in various photocatalytic processes is constrained by the rapid recombination of photogenerated charge carriers. In this study, 1D/2D Schottky junctions were fabricated to mitigate the recombination phenomenon by combining WO₃ nanorods (WRs) with small quantities of Ti3C2Tx MXene. The morphological, structural, and optical properties of the composite materials were examined using various characterization techniques. Furthermore, their photocatalytic performance under simulated solar light was assessed by monitoring the degradation of the insecticide Clothianidin, which served as a model emerging contaminant. The results indicated that the incorporation of 5% W/W Ti3C2Tx with WRs significantly enhances photocatalytic efficiency by approximately 50%. This improvement was attributed to the migration of photogenerated electrons to the Fermi level (Ef) of the MXene, leading to the formation of a Schottky barrier at the interface between the two materials, which impedes electron backflow. Therefore, recombination between positive holes and photogenerated electrons was effectively suppressed, as evidenced by photoluminescence spectroscopy. Scavenging experiments demonstrated that hydroxyl radicals are the primary reactive species involved in the degradation of Clothianidin, with positive holes contributing to a lesser extent. Overall, the findings of this study highlight the potential of MXenes, such as Ti₃C₂Tx, to enhance the photocatalytic efficiency of WO₃ nanorods via the formation of Schottky junctions. This advancement promotes the application of these photocatalytic materials in large-scale processes associated with wastewater remediation and green fuel production.
{"title":"Fabrication of 1D/2D WO3 nanorods@Ti3C2Tx Schottky junctions for photocatalytic removal of the insecticide Clothianidin from aqueous matrices","authors":"Christos Lykos , Charalampos Drivas , Mark A. Isaacs , Kalliopi Ladomenou , George Z. Kyzas , Triantafyllos Albanis , Ioannis Konstantinou","doi":"10.1016/j.mcat.2025.115656","DOIUrl":"10.1016/j.mcat.2025.115656","url":null,"abstract":"<div><div>Tungsten trioxide (WO₃) is an n-type semiconductor with a relatively narrow band gap, which enables its photoactivation under visible light. However, its application in various photocatalytic processes is constrained by the rapid recombination of photogenerated charge carriers. In this study, 1D/2D Schottky junctions were fabricated to mitigate the recombination phenomenon by combining WO₃ nanorods (WRs) with small quantities of Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> MXene. The morphological, structural, and optical properties of the composite materials were examined using various characterization techniques. Furthermore, their photocatalytic performance under simulated solar light was assessed by monitoring the degradation of the insecticide Clothianidin, which served as a model emerging contaminant. The results indicated that the incorporation of 5% <sup>W</sup>/<sub>W</sub> Ti<sub>3</sub>C<sub>2</sub>T<sub>x</sub> with WRs significantly enhances photocatalytic efficiency by approximately 50%. This improvement was attributed to the migration of photogenerated electrons to the Fermi level (E<sub>f</sub>) of the MXene, leading to the formation of a Schottky barrier at the interface between the two materials, which impedes electron backflow. Therefore, recombination between positive holes and photogenerated electrons was effectively suppressed, as evidenced by photoluminescence spectroscopy. Scavenging experiments demonstrated that hydroxyl radicals are the primary reactive species involved in the degradation of Clothianidin, with positive holes contributing to a lesser extent. Overall, the findings of this study highlight the potential of MXenes, such as Ti₃C₂Tx, to enhance the photocatalytic efficiency of WO₃ nanorods via the formation of Schottky junctions. This advancement promotes the application of these photocatalytic materials in large-scale processes associated with wastewater remediation and green fuel production.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115656"},"PeriodicalIF":4.9,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734053","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 development of catalysts for the selective oxidation of biomass-based alcohols in order to increase valorization of lignin is an urgent task in the transition to renewable sources of hydrocarbons. In this work, catalysts based on VC with a core-shell structure have been obtained by microwave irradiation. This synthesis method makes it possible to produce carbide catalysts using inexpensive equipment in an extremely short time (15 min). The VCm.b. catalyst exhibits remarkable activity in the aerobic oxidation reaction of benzyl alcohol with 100 % aldehyde selectivity. It was found that VC catalyst contains the surface oxovanadium species in various states, a large number of oxygen vacancies acts as Lewis’s acid sites, and has high acidic properties that promote effective oxidation of aromatic alcohols. The VCm.b. catalyst demonstrates a 5–7-fold increase in oxidation rate compared to analogues based on noble metals, as well as the possibility of recycling for at least 5 cycles. It is shown that the VCm.b. catalyst can effectively oxidize benzyl alcohol to benzaldehyde using air under optimal conditions: 140 °C, 1 h, 8 atm, 4.3 mg/mL VCm.b., 0.5 wt.% substrate. It is noted that surface oxovanadium sites are capable of strongly chemisorbing particles whose atoms are electron pair donors, including methoxy substituted aromatic alcohols, leading to the effect of irreversible adsorption. Mechanism studies reveal that the aerobic oxidation of benzyl alcohol into the corresponding aldehyde can proceed using chemosorbed oxygen on the catalyst surface, and atmospheric oxygen is activated to form the superoxide radical O2•- and singlet oxygen 1O2.
{"title":"Facilitated aerobic oxidation of lignin model alcohols over microwave-synthesized vanadium carbide core-shell catalysts with oxovanadium active shell","authors":"M.O. Lukashov , E.A. Eseva , V.D. Elsesser , D.D. Davtyan , A.M. Aghoyan , K.A. Cherednichenko , Y.V. Timchenko , I.A. Rodin , A.V. Akopyan","doi":"10.1016/j.mcat.2025.115633","DOIUrl":"10.1016/j.mcat.2025.115633","url":null,"abstract":"<div><div>The development of catalysts for the selective oxidation of biomass-based alcohols in order to increase valorization of lignin is an urgent task in the transition to renewable sources of hydrocarbons. In this work, catalysts based on VC with a core-shell structure have been obtained by microwave irradiation. This synthesis method makes it possible to produce carbide catalysts using inexpensive equipment in an extremely short time (15 min). The VC<sub>m.b.</sub> catalyst exhibits remarkable activity in the aerobic oxidation reaction of benzyl alcohol with 100 % aldehyde selectivity. It was found that VC catalyst contains the surface oxovanadium species in various states, a large number of oxygen vacancies acts as Lewis’s acid sites, and has high acidic properties that promote effective oxidation of aromatic alcohols. The VC<sub>m.b.</sub> catalyst demonstrates a 5–7-fold increase in oxidation rate compared to analogues based on noble metals, as well as the possibility of recycling for at least 5 cycles. It is shown that the VC<sub>m.b.</sub> catalyst can effectively oxidize benzyl alcohol to benzaldehyde using air under optimal conditions: 140 °C, 1 h, 8 atm, 4.3 mg/mL VC<sub>m.b.</sub>, 0.5 wt.% substrate. It is noted that surface oxovanadium sites are capable of strongly chemisorbing particles whose atoms are electron pair donors, including methoxy substituted aromatic alcohols, leading to the effect of irreversible adsorption. Mechanism studies reveal that the aerobic oxidation of benzyl alcohol into the corresponding aldehyde can proceed using chemosorbed oxygen on the catalyst surface, and atmospheric oxygen is activated to form the superoxide radical O<sub>2</sub><sup>•-</sup> and singlet oxygen <sup>1</sup>O<sub>2</sub>.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115633"},"PeriodicalIF":4.9,"publicationDate":"2025-12-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734548","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 : 2025-12-08DOI: 10.1016/j.mcat.2025.115642
Zeyu Liu , Lu Wang , Haijun Yan , Shahid Ali , Chao Yang , Ronglan Wu , Jide Wang , Yana Wei , Hui Sun , Changhai Liang
In response to the stringent mercury restrictions of the Minamata Convention, replacing mercury-based catalysts with precious metal alternatives for polyvinyl chloride (PVC) production has become imperative. However, the deactivation of Pd-based catalysts poses a significant challenge for acetylene hydrochlorination. Herein, a graphitic carbon nitride (g-C3N4)-modified activated carbon (AC) support to stabilize Pd catalysts was reported and the optimized Pd-g-C3N4/AC catalyst exhibited exceptional activity, achieving 95 % acetylene conversion and 99 % vinyl chloride selectivity for over 10 h. Combined characterization and density functional theory (DFT) simulations revealed that the g-C3N4 incorporation modulates the microelectronic environment of Pd active sites, thereby balancing the adsorption energy difference between acetylene and hydrogen chloride on the catalyst surface. This balance enables the reactants to participate in the reaction in a timely manner, which is identified as the fundamental mechanism behind the improved catalytic stability. This work offers a design strategy for high-performance, mercury-free Pd-based catalysts for acetylene hydrochlorination.
{"title":"Enhanced catalytic performance of palladium supported on graphitic carbon nitride for acetylene hydrochlorination","authors":"Zeyu Liu , Lu Wang , Haijun Yan , Shahid Ali , Chao Yang , Ronglan Wu , Jide Wang , Yana Wei , Hui Sun , Changhai Liang","doi":"10.1016/j.mcat.2025.115642","DOIUrl":"10.1016/j.mcat.2025.115642","url":null,"abstract":"<div><div>In response to the stringent mercury restrictions of the Minamata Convention, replacing mercury-based catalysts with precious metal alternatives for polyvinyl chloride (PVC) production has become imperative. However, the deactivation of Pd-based catalysts poses a significant challenge for acetylene hydrochlorination. Herein, a graphitic carbon nitride (g-C<sub>3</sub>N<sub>4</sub>)-modified activated carbon (AC) support to stabilize Pd catalysts was reported and the optimized Pd-g-C<sub>3</sub>N<sub>4</sub>/AC catalyst exhibited exceptional activity, achieving 95 % acetylene conversion and 99 % vinyl chloride selectivity for over 10 h. Combined characterization and density functional theory (DFT) simulations revealed that the g-C<sub>3</sub>N<sub>4</sub> incorporation modulates the microelectronic environment of Pd active sites, thereby balancing the adsorption energy difference between acetylene and hydrogen chloride on the catalyst surface. This balance enables the reactants to participate in the reaction in a timely manner, which is identified as the fundamental mechanism behind the improved catalytic stability. This work offers a design strategy for high-performance, mercury-free Pd-based catalysts for acetylene hydrochlorination.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115642"},"PeriodicalIF":4.9,"publicationDate":"2025-12-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734052","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 : 2025-12-07DOI: 10.1016/j.mcat.2025.115653
Shuai Zhang , Xuejian Zhang , Ke Li , Kangzhou Wang , Caihu Li , Xinhua Gao , Qingxiang Ma , Tian-Sheng Zhao , Jianli Zhang
Fischer-Tropsch synthesis (FTS) is a key process for the catalytic conversion of carbon containing resources into liquid fuels and high-value chemicals. Regulating product distribution to achieve highly selective olefin production via FTS over Fe-based catalysts is of great research significance. In this study, a surface oxidation strategy was adopted to achieve surface functionalization of Fe/g-C3N4, and the regulatory mechanisms of surface groups introduced by different oxidants on the textural properties, surface characteristics, reduction and adsorption behaviors, as well as the catalytic performance of Fe/g-C3N4 in CO hydrogenation were systematically investigated. The results indicate that HNO3 treatment can promote the conversion of pyridinic N to pyrrolic N ing-C3N4, and enhance the reducibility and carburization of iron species. In CO hydrogenation, the Fe/g-C3N4-HNO3 catalyst exhibits a high olefin/paraffin ratio (O/P=4.91) and C2–4= selectivity (49.54%) in the absence of any alkali metal modification. The strong electronic effect of pyrrolic N significantly enhanced the olefin selectivity and chain propagation of the Fe-based catalyst in FTS.
{"title":"Surface functionalization of Fe/g-C3N4 for highly selective formation of light olefins in Fischer-Tropsch synthesis","authors":"Shuai Zhang , Xuejian Zhang , Ke Li , Kangzhou Wang , Caihu Li , Xinhua Gao , Qingxiang Ma , Tian-Sheng Zhao , Jianli Zhang","doi":"10.1016/j.mcat.2025.115653","DOIUrl":"10.1016/j.mcat.2025.115653","url":null,"abstract":"<div><div>Fischer-Tropsch synthesis (FTS) is a key process for the catalytic conversion of carbon containing resources into liquid fuels and high-value chemicals. Regulating product distribution to achieve highly selective olefin production via FTS over Fe-based catalysts is of great research significance. In this study, a surface oxidation strategy was adopted to achieve surface functionalization of Fe/g-C<sub>3</sub>N<sub>4</sub>, and the regulatory mechanisms of surface groups introduced by different oxidants on the textural properties, surface characteristics, reduction and adsorption behaviors, as well as the catalytic performance of Fe/g-C<sub>3</sub>N<sub>4</sub> in CO hydrogenation were systematically investigated. The results indicate that HNO<sub>3</sub> treatment can promote the conversion of pyridinic N to pyrrolic N ing-C<sub>3</sub>N<sub>4</sub>, and enhance the reducibility and carburization of iron species. In CO hydrogenation, the Fe/g-C<sub>3</sub>N<sub>4</sub>-HNO<sub>3</sub> catalyst exhibits a high olefin/paraffin ratio (O/P=4.91) and C<sub>2–4</sub><sup>=</sup> selectivity (49.54%) in the absence of any alkali metal modification. The strong electronic effect of pyrrolic N significantly enhanced the olefin selectivity and chain propagation of the Fe-based catalyst in FTS.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115653"},"PeriodicalIF":4.9,"publicationDate":"2025-12-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145734556","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 : 2025-12-06DOI: 10.1016/j.mcat.2025.115654
Maria V. Nenasheva , Bogdan O. Protsenko , Kirill D. Kulaev , Evgeny R. Naranov , Alexander L. Trigub , Anton L. Maximov , Alexander A. Guda , Dmitry N. Gorbunov
The design of novel active and stable heterogeneous catalysts for industrially important hydroformylation reaction is a challenging task. In our study, we report the first non-phosphoric polyurethane-based hydroformylation catalyst, which is also active in hydrogenation of aldehydes under hydroformylation conditions for one-step transformation of olefins to primary alcohols. The catalyst was found to be active in the reductive hydroformylation of the model substrate (1-hexene), as well as a range of other unsaturated substrates. At longer reaction times, alcohols were the dominant products. Also, the catalyst showed a sufficient reusability. We prove that Rh atoms in the catalyst are present in the form of highly coordinated complexes both before and after reductive hydroformylation. Based on the in situ Rh K-edge X-ray absorption spectroscopy we propose the structure of Rh active sites.
{"title":"Polyurethane-based heterogeneous catalysts with highly dispersed Rh single sites for reductive hydroformylation of olefins","authors":"Maria V. Nenasheva , Bogdan O. Protsenko , Kirill D. Kulaev , Evgeny R. Naranov , Alexander L. Trigub , Anton L. Maximov , Alexander A. Guda , Dmitry N. Gorbunov","doi":"10.1016/j.mcat.2025.115654","DOIUrl":"10.1016/j.mcat.2025.115654","url":null,"abstract":"<div><div>The design of novel active and stable heterogeneous catalysts for industrially important hydroformylation reaction is a challenging task. In our study, we report the first non-phosphoric polyurethane-based hydroformylation catalyst, which is also active in hydrogenation of aldehydes under hydroformylation conditions for one-step transformation of olefins to primary alcohols. The catalyst was found to be active in the reductive hydroformylation of the model substrate (1-hexene), as well as a range of other unsaturated substrates. At longer reaction times, alcohols were the dominant products. Also, the catalyst showed a sufficient reusability. We prove that Rh atoms in the catalyst are present in the form of highly coordinated complexes both before and after reductive hydroformylation. Based on the in situ Rh K-edge X-ray absorption spectroscopy we propose the structure of Rh active sites.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115654"},"PeriodicalIF":4.9,"publicationDate":"2025-12-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692259","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 : 2025-12-05DOI: 10.1016/j.mcat.2025.115650
Lu Wang, Yongheng Li, He Chen, Xingyong Wang, Hongchen Li, Ruoqian Zhang, Songbao Fu
This study utilized DFT methods to examine whether binuclear Pd sites confined in SSZ-13 could provide a feasible pathway for the direct decomposition of NO. Based on previous observations suggesting that SSZ-13 with a Si/Al ratio of 10:1 provides a representative coordination environment, a corresponding structural model was constructed. Bridge configurations of Pd(0), Pd(I), and Pd(II) located within either eight-membered or six-membered rings were then evaluated. Model screening and mechanistic analysis revealed that binuclear Pd bridges in eight-membered rings are significantly more stable, whereas those in six-membered rings tend to break apart. The intrinsic mechanistic behaviors of Pd species with different oxidation states were analyzed in detail, with particular emphasis on how variations in electron-donating capability influence NO adsorption, ONNO formation, NO bond cleavage, and subsequent steps of the reaction cycle. Among the examined configurations, Pd(I) exhibits the most favorable intrinsic energetics for the elementary steps of NO decomposition. Kinetic analysis based on TST further confirmed the intrinsic trend Pd(I) > Pd(0) > Pd(II), consistent with qualitative observations of pseudo-metallic Pd species in previous experimental studies. Meanwhile, N2O formation and oxygen accumulation were identified as key factors that could promote oxidative deactivation. These theoretical insights will provide predictive guidance for future experimental investigations into the reactivity of Pd sites in SSZ-13.
{"title":"Exploring the potential reactivity of binuclear Pd active sites in NO direct decomposition on Pd/SSZ-13: A DFT study","authors":"Lu Wang, Yongheng Li, He Chen, Xingyong Wang, Hongchen Li, Ruoqian Zhang, Songbao Fu","doi":"10.1016/j.mcat.2025.115650","DOIUrl":"10.1016/j.mcat.2025.115650","url":null,"abstract":"<div><div>This study utilized DFT methods to examine whether binuclear Pd sites confined in SSZ-13 could provide a feasible pathway for the direct decomposition of NO. Based on previous observations suggesting that SSZ-13 with a Si/Al ratio of 10:1 provides a representative coordination environment, a corresponding structural model was constructed. Bridge configurations of Pd(0), Pd(I), and Pd(II) located within either eight-membered or six-membered rings were then evaluated. Model screening and mechanistic analysis revealed that binuclear Pd bridges in eight-membered rings are significantly more stable, whereas those in six-membered rings tend to break apart. The intrinsic mechanistic behaviors of Pd species with different oxidation states were analyzed in detail, with particular emphasis on how variations in electron-donating capability influence NO adsorption, ONNO formation, N<img>O bond cleavage, and subsequent steps of the reaction cycle. Among the examined configurations, Pd(I) exhibits the most favorable intrinsic energetics for the elementary steps of NO decomposition. Kinetic analysis based on TST further confirmed the intrinsic trend Pd(I) > Pd(0) > Pd(II), consistent with qualitative observations of pseudo-metallic Pd species in previous experimental studies. Meanwhile, N<sub>2</sub>O formation and oxygen accumulation were identified as key factors that could promote oxidative deactivation. These theoretical insights will provide predictive guidance for future experimental investigations into the reactivity of Pd sites in SSZ-13.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"590 ","pages":"Article 115650"},"PeriodicalIF":4.9,"publicationDate":"2025-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145692313","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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