Pub Date : 2025-04-05DOI: 10.1016/j.jcat.2025.116117
Ziyuan Yan , Xiaoning Li , Xinwei Guan , Zhaoliang Wang , Jinni Shen , Tingjiang Yan , Tianyi Ma , Zizhong Zhang
The photocatalytic nonoxidative coupling of methane (CH4) is crucial for sustainable energy production and chemical synthesis, however, a key challenge in advancing this process lies in the development of efficient and highly selective catalytic systems. In this study, we employ an in situ thermally induced strategy to promote the in-situ growth of oxygen vacancies (VO) for constructing a high-density In-VO-In-OH frustrated Lewis pairs (FLP) on Ag/In(OH)3-InOOH (Ag/InOxHy). Our results demonstrate that FLP can effectively polarize C–H bonds, while Ag nanoparticles serve as electron acceptors, significantly reducing the recombination of photogenerated carriers and enhancing the catalytic performance of methane coupling. Benefiting from the high density of FLP and photothermal synergistic effect, we achieve a remarkable C2H6 yield of 339.2 μmol gcat−1h−1 over Ag/InOxHy in a flow methane atmosphere. Notably, in-situ electron paramagnetic resonance analysis not only validates this innovative strategy but also reveals a new mechanism of oxygen vacancy recycling which showcases its great potential to advance other photocatalytic processes.
{"title":"Boosting photothermal catalytic non-oxidative methane coupling by high-density frustrated Lewis pairs in Ag/InOxHy","authors":"Ziyuan Yan , Xiaoning Li , Xinwei Guan , Zhaoliang Wang , Jinni Shen , Tingjiang Yan , Tianyi Ma , Zizhong Zhang","doi":"10.1016/j.jcat.2025.116117","DOIUrl":"10.1016/j.jcat.2025.116117","url":null,"abstract":"<div><div>The photocatalytic nonoxidative coupling of methane (CH<sub>4</sub>) is crucial for sustainable energy production and chemical synthesis, however, a key challenge in advancing this process lies in the development of efficient and highly selective catalytic systems. In this study, we employ an in situ thermally induced strategy to promote the in-situ growth of oxygen vacancies (V<sub>O</sub>) for constructing a high-density In-V<sub>O</sub>-In-OH frustrated Lewis pairs (FLP) on Ag/In(OH)<sub>3</sub>-InOOH (Ag/InO<sub>x</sub>H<sub>y</sub>). Our results demonstrate that FLP can effectively polarize C–H bonds, while Ag nanoparticles serve as electron acceptors, significantly reducing the recombination of photogenerated carriers and enhancing the catalytic performance of methane coupling. Benefiting from the high density of FLP and photothermal synergistic effect, we achieve a remarkable C<sub>2</sub>H<sub>6</sub> yield of 339.2 μmol g<sub>cat</sub><sup>−1</sup>h<sup>−1</sup> over Ag/InO<sub>x</sub>H<sub>y</sub> in a flow methane atmosphere. Notably, in-situ electron<!--> <!-->paramagnetic resonance analysis not only validates this innovative strategy but also reveals a new mechanism of oxygen vacancy recycling which showcases its great potential to advance other photocatalytic processes.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116117"},"PeriodicalIF":6.5,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782771","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-04DOI: 10.1016/j.jcat.2025.116114
Mengyuan Zhang , Kongliang Luo , Peixuan Li , Hailong Li , Chuandong He , Junjun Zhang , Qiang Niu , Pengfei Zhang
Currently, using Density Functional Theory (DFT) to drive the synthesis of targeted oxygen evolution reaction (OER) catalysts, has attracted strong attention. Herein, sulfides were selected as the models. First, the density of states (DOS), active sites and the Gibbs free energy of intermediates (ΔG) of different models were calculated respectively. DFT results indicated that d-band centers of models with sulfur vacancies, self-reconstruction, or high entropy structures possessing lower ΔGmax, being closer to the Fermi level, exhibiting higher DOS at the Fermi level. To verify DFT results, thiourea was used as a precursor to prepare (CrMnCoNiMo)0.2Sx for the first time. Indeed, (CrMnCoNiMo)0.2Sx exhibited excellent OER activity (η100 = 266 mV, Tafel slope = 57.4 mV dec−1) and strong catalytic stability. The sulfur vacancies were confirmed by EPR experiments. TEM, XPS and ICP-AES all confirmed the leaching of Cr and Mo elements after OER. XPS, TEM and In situ Raman confirmed the self-reconstruction of (CrMnCoNiMo)0.2Sx during the OER. The above experimental results perfectly confirmed the initial DFT calculation.
{"title":"Design targeted high entropy sulfides catalysts for OER by theoretical predictions","authors":"Mengyuan Zhang , Kongliang Luo , Peixuan Li , Hailong Li , Chuandong He , Junjun Zhang , Qiang Niu , Pengfei Zhang","doi":"10.1016/j.jcat.2025.116114","DOIUrl":"10.1016/j.jcat.2025.116114","url":null,"abstract":"<div><div>Currently, using Density Functional Theory (DFT) to drive the synthesis of targeted oxygen evolution reaction (OER) catalysts, has attracted strong attention. Herein, sulfides were selected as the models. First, the density of states (DOS), active sites and the Gibbs free energy of intermediates (ΔG) of different models were calculated respectively. DFT results indicated that d-band centers of models with sulfur vacancies, self-reconstruction, or high entropy structures possessing lower ΔG<sub>max</sub>, being closer to the Fermi level, exhibiting higher DOS at the Fermi level. To verify DFT results, thiourea was used as a precursor to prepare (CrMnCoNiMo)<sub>0.2</sub>S<sub>x</sub> for the first time. Indeed, (CrMnCoNiMo)<sub>0.2</sub>S<sub>x</sub> exhibited excellent OER activity (η<sub>100</sub> = 266 mV, Tafel slope = 57.4 mV dec<sup>−1</sup>) and strong catalytic stability. The sulfur vacancies were confirmed by EPR experiments. TEM, XPS and ICP-AES all confirmed the leaching of Cr and Mo elements after OER. XPS, TEM and In situ Raman confirmed the self-reconstruction of (CrMnCoNiMo)<sub>0.2</sub>S<sub>x</sub> during the OER. The above experimental results perfectly confirmed the initial DFT calculation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116114"},"PeriodicalIF":6.5,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782772","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The photocatalytic ammonia synthesis provides a promising alternative for the sustainable production of ammonia. However, poor separation efficiency of photoinduced carriers and insufficient activation of N2 remain the key obstacles to high-performance N2 reduction. Herein, a MOF-on-MOF-derived material with a Z-scheme heterojunction has been reported. The Brunauer-Emmett-Teller (BET) and electrochemical impedance spectroscopy (EIS) analyses indicate that the coexistence of the two MOFs accelerates the mass transfer process at the gas-solid-liquid interface and promotes the diffusion process of nitrogen molecules to the heterogeneous interface, thereby facilitating the adsorption of N2. According to analyses of Diffuse Reflectance Spectroscopy (DRS), Mott-Schottky (M−S) and density functional theory (DFT), the MIL-101(Fe)/ZIF-67 derived material (MZ-600) complies with the charge transfer mechanism of the Z-scheme heterojunction, which realizes the effective separation of photogenerated carriers and preserves the strong redox capacity of electrons and holes. Meanwhile, it stimulates the activation of the N≡N bond and lowers the energy barrier of the rate determining step(*N2→*N2H). Therefore, the rationally designed MZ-600 heterojunction exhibits remarkable PNRR performance, with an NH3 yield of 103.90 μmol·g−1·h−1 and an apparent quantum yield (AQY) of 1.17 % at 465 nm. Moreover, compared to catalyst powder, the MZ-600 catalyst supported on vertical carbon paper can decrease recontamination and is convenient to be recycled.
{"title":"Construction of MOF-on-MOF-derived composites with coexisting octahedrons and dodecahedrons for superior photocatalytic nitrogen fixation","authors":"Runxian Hao , Zaihang Zheng , Yixin Li, Meili Zheng, Songquan Pan, Jie Hu, Hao Huang","doi":"10.1016/j.jcat.2025.116121","DOIUrl":"10.1016/j.jcat.2025.116121","url":null,"abstract":"<div><div>The photocatalytic ammonia synthesis provides a promising alternative for the sustainable production of ammonia. However, poor separation efficiency of photoinduced carriers and insufficient activation of N<sub>2</sub> remain the key obstacles to high-performance N<sub>2</sub> reduction. Herein, a MOF-on-MOF-derived material with a Z-scheme heterojunction has been reported. The Brunauer-Emmett-Teller (BET) and electrochemical impedance spectroscopy (EIS) analyses indicate that the coexistence of the two MOFs accelerates the mass transfer process at the gas-solid-liquid interface and promotes the diffusion process of nitrogen molecules to the heterogeneous interface, thereby facilitating the adsorption of N<sub>2</sub>. According to analyses of Diffuse Reflectance Spectroscopy (DRS), Mott-Schottky (M−S) and density functional theory (DFT), the MIL-101(Fe)/ZIF-67 derived material (MZ-600) complies with the charge transfer mechanism of the Z-scheme heterojunction, which realizes the effective separation of photogenerated carriers and preserves the strong redox capacity of electrons and holes. Meanwhile, it stimulates the activation of the N≡N bond and lowers the energy barrier of the rate determining step(*N<sub>2</sub>→*N<sub>2</sub>H). Therefore, the rationally designed MZ-600 heterojunction exhibits remarkable PNRR performance, with an NH<sub>3</sub> yield of 103.90 μmol·g<sup>−1</sup>·h<sup>−1</sup> and an apparent quantum yield (AQY) of 1.17 % at 465 nm. Moreover, compared to catalyst powder, the MZ-600 catalyst supported on vertical carbon paper can decrease recontamination and is convenient to be recycled.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116121"},"PeriodicalIF":6.5,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782775","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-04DOI: 10.1016/j.jcat.2025.116123
Maosen Xu , Shanshan Zhao , Jinhua Feng , Yunzheng Deng , Yuemeng Ji , Yingxin Yu , Hongli Liu , Taicheng An
In-depth dissecting the activation of C-Cl bonds and the migration transformation of dissociated chlorine species is significant to understand the mechanism underlying the formation of polychlorinated by products and chlorine poisoning deactivation of catalyst during of the photocatalytic degradation of chlorinated volatile organic compounds (CVOCs). Herein, carbon nanolayers wrapped TiO2 composites (CTO), and its contrastive catalysts including defective carbon nanolayers wrapped TiO2 (DCTO) and TiO2 without carbon nanolayer (TO) are constructed by rational pyrolysis of titanium-based MOFs. The obtained CTO exhibits a remarkable degradation efficiency of up to 91.74 % for CH2Cl2 after 3 h of UV–vis irradiation, robust stability as well as water resistance, far superior to that of DCTO and TO. Density functional theory calculations combined with in-situ XPS reveal that the heterogeneous interface interactions between carbon nanolayers and TiO2 greatly facilitate the separation of photogenerated carriers, boosting the redox capacity of CTO. Simultaneously, the dissociated Cl species from the cleavage of the C-Cl bond can be preferentially adsorbed onto the outer carbon nanolayers, thereby inhibiting the occupation of TiO2 active sites by chlorine. The preferential adsorption sites of the dissociated Cl species and optimized deep oxidation ability synergistically boost the catalytic performance and resistance of chlorine poisoning and inhibit the production of polychlorinated by-products.
{"title":"Optimizing photocatalytic degradation of dichloromethane by MOF-derived TiO2/C catalyst: Unraveling the decisive role of carbon nanolayers and reaction mechanism","authors":"Maosen Xu , Shanshan Zhao , Jinhua Feng , Yunzheng Deng , Yuemeng Ji , Yingxin Yu , Hongli Liu , Taicheng An","doi":"10.1016/j.jcat.2025.116123","DOIUrl":"10.1016/j.jcat.2025.116123","url":null,"abstract":"<div><div>In-depth dissecting the activation of C-Cl bonds and the migration transformation of dissociated chlorine species is significant to understand the mechanism underlying the formation of polychlorinated by products and chlorine poisoning deactivation of catalyst during of the photocatalytic degradation of chlorinated volatile organic compounds (CVOCs). Herein, carbon nanolayers wrapped TiO<sub>2</sub> composites (CTO), and its contrastive catalysts including defective carbon nanolayers wrapped TiO<sub>2</sub> (DCTO) and TiO<sub>2</sub> without carbon nanolayer (TO) are constructed by rational pyrolysis of titanium-based MOFs. The obtained CTO exhibits a remarkable degradation efficiency of up to 91.74 % for CH<sub>2</sub>Cl<sub>2</sub> after 3 h of UV–vis irradiation, robust stability as well as water resistance, far superior to that of DCTO and TO. Density functional theory calculations combined with <em>in-situ</em> XPS reveal that the heterogeneous interface interactions between carbon nanolayers and TiO<sub>2</sub> greatly facilitate the separation of photogenerated carriers, boosting the redox capacity of CTO. Simultaneously, the dissociated Cl species from the cleavage of the C-Cl bond can be preferentially adsorbed onto the outer carbon nanolayers, thereby inhibiting the occupation of TiO<sub>2</sub> active sites by chlorine. The preferential adsorption sites of the dissociated Cl species and optimized deep oxidation ability synergistically boost the catalytic performance and resistance of chlorine poisoning and inhibit the production of polychlorinated by-products.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116123"},"PeriodicalIF":6.5,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782974","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-04DOI: 10.1016/j.jcat.2025.116122
Dalei Sun , Hongyu Li , Chen Zhou , Jinghui Cai , Zhi-Wu Liang
The photothermal catalytic carbonylation of n-alkylamine with CO2 is one of the most promising “carbon neutral” pathways due to the coupling of CO2 capture and conversion. And the development of high-performance catalysts is vital to the reaction due to the inherent chemical inertness of CO2. Herein, Co-Ce composite oxides with rich oxygen vacancy (Ov) were successfully synthesized via hydrothermal method and applied firstly to photothermal catalytic carbonylation of n-butyl amine with CO2. As optimizing the molar ratio of Co3O4/CeO2, Co3O4/CeO2-0.4 with up to both 95.51 % of n-butylamine conversion and 94.50 % of N,N′-dibutylurea were obtained in the presence of PEG 400 solvent using 500 W Xe lamp as the light source under 110 ℃ and 1.0 MPa for 4 h, respectively. Further characterizations such as XRD, BET, Raman, XPS, CO2/NH3-TPD, UV–Vis, PL and TPC show that both the high photocurrent density and Ov-rich content on the surface of Co3O4/CeO2-0.4 enhances the adsorption-activation of CO2 by facilitating the migration of d electrons from the active sites to the 2π antibonding orbitals of CO2. Finally, a Lewis acid-base interactions mechanism was also proposed in the photothermal catalytic carbonylation of amine by CO2 over the Co-Ce complex oxides.
{"title":"Enhanced photothermal catalytic activity of CeO2 through Co-modified for the carbonylation of amine with CO2","authors":"Dalei Sun , Hongyu Li , Chen Zhou , Jinghui Cai , Zhi-Wu Liang","doi":"10.1016/j.jcat.2025.116122","DOIUrl":"10.1016/j.jcat.2025.116122","url":null,"abstract":"<div><div>The photothermal catalytic carbonylation of n-alkylamine with CO<sub>2</sub> is one of the most promising “carbon neutral” pathways due to the coupling of CO<sub>2</sub> capture and conversion. And the development of high-performance catalysts is vital to the reaction due to the inherent chemical inertness of CO<sub>2</sub>. Herein, Co-Ce composite oxides with rich oxygen vacancy (O<sub>v</sub>) were successfully synthesized via hydrothermal method and applied firstly to photothermal catalytic carbonylation of n-butyl amine with CO<sub>2</sub>. As optimizing the molar ratio of Co<sub>3</sub>O<sub>4</sub>/CeO<sub>2</sub>, Co<sub>3</sub>O<sub>4</sub>/CeO<sub>2</sub>-0.4 with up to both 95.51 % of n-butylamine conversion and 94.50 % of N,N′-dibutylurea were obtained in the presence of PEG 400 solvent using 500 W Xe lamp as the light source under 110 ℃ and 1.0 MPa for 4 h, respectively. Further characterizations such as XRD, BET, Raman, XPS, CO<sub>2</sub>/NH<sub>3</sub>-TPD, UV–Vis, PL and TPC show that both the high photocurrent density and O<sub>v</sub>-rich content on the surface of Co<sub>3</sub>O<sub>4</sub>/CeO<sub>2</sub>-0.4 enhances the adsorption-activation of CO<sub>2</sub> by facilitating the migration of d electrons from the active sites to the 2π antibonding orbitals <strong>of</strong> CO<sub>2</sub>. Finally, a Lewis acid-base interactions mechanism was also proposed in the photothermal catalytic carbonylation of amine by CO<sub>2</sub> over the Co-Ce complex oxides.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116122"},"PeriodicalIF":6.5,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143782773","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
A novel photoreactive composite consisting of CuO-loaded N-doped TiO2 (CuNdT) embedded in a syndiotactic polystyrene (sPS) monolithic aerogel was developed and evaluated for the photocatalytic hydroxylation of benzene to phenol under visible light irradiation. The process was identified as biphasic, where the photoreaction occurred within the solid phase of the composite, and the surrounding liquid phase acted as a reservoir for the desired product (phenol). The composite was extensively characterized through WAXD, SEM, BET, and tomographic analyses, confirming the uniform dispersion of CuNdT particles within the porous, hydrophobic sPS matrix. Under acidic conditions (pH = 2), the composite achieved 96 % benzene conversion and >99 % phenol selectivity within 180 min of irradiation, results that surpass those reported in the literature for visible-light-driven benzene hydroxylation. Kinetic modeling, based on experimentally determined partition coefficients for benzene and phenol, revealed that the composite operated entirely in a chemical regime, free from diffusional limitations. The calculated efficiency factors, all equal to 1, confirmed that the reaction was controlled solely by chemical processes occurring on the CuNdT dispersed inside the sPS matrix. The differences in kinetic constants between pH = 7 and pH = 2 highlighted the critical role of pH in driving the photocatalytic process. At pH = 2, the increased tendency of H2O2 to form hydroxyl radicals enhanced the rates of benzene consumption and phenol formation. Additionally, the higher affinity of benzene for the hydrophobic sPS polymer matrix at acidic pH, as reflected by its elevated partition coefficient, further facilitated its interaction with the composite, promoting faster oxidation. In contrast, phenol displayed a lower affinity for the hydrophobic sPS matrix at pH = 2, as evidenced by its lower partition coefficient, allowing it to remain in the liquid phase, reducing over-oxidation and contributing to the higher phenol yield (96 %) observed at acidic pH. This synergistic effect between enhanced hydroxyl radical generation, increased benzene affinity and reduced phenol affinity led to a more efficient photocatalytic process under acidic conditions. These findings establish CuNdT/sPS as a highly efficient, selective, and robust photocatalytic material, combining superior performance, structural stability, and excellent reusability for multiple reaction cycles.
{"title":"Simultaneous boosting visible light-driven benzene hydroxylation reaction rate and phenol selectivity via a novel monolithic polymer photoreactive composite based on N-doped TiO2 supported CuO","authors":"Antonietta Mancuso , Olga Sacco , Vincenzo Vaiano , Vincenzo Venditto","doi":"10.1016/j.jcat.2025.116116","DOIUrl":"10.1016/j.jcat.2025.116116","url":null,"abstract":"<div><div>A novel photoreactive composite consisting of CuO-loaded N-doped TiO<sub>2</sub> (CuNdT) embedded in a syndiotactic polystyrene (sPS) monolithic aerogel was developed and evaluated for the photocatalytic hydroxylation of benzene to phenol under visible light irradiation. The process was identified as biphasic, where the photoreaction occurred within the solid phase of the composite, and the surrounding liquid phase acted as a reservoir for the desired product (phenol). The composite was extensively characterized through WAXD, SEM, BET, and tomographic analyses, confirming the uniform dispersion of CuNdT particles within the porous, hydrophobic sPS matrix. Under acidic conditions (pH = 2), the composite achieved 96 % benzene conversion and >99 % phenol selectivity within 180 min of irradiation, results that surpass those reported in the literature for visible-light-driven benzene hydroxylation. Kinetic modeling, based on experimentally determined partition coefficients for benzene and phenol, revealed that the composite operated entirely in a chemical regime, free from diffusional limitations. The calculated efficiency factors, all equal to 1, confirmed that the reaction was controlled solely by chemical processes occurring on the CuNdT dispersed inside the sPS matrix. The differences in kinetic constants between pH = 7 and pH = 2 highlighted the critical role of pH in driving the photocatalytic process. At pH = 2, the increased tendency of H<sub>2</sub>O<sub>2</sub> to form hydroxyl radicals enhanced the rates of benzene consumption and phenol formation. Additionally, the higher affinity of benzene for the hydrophobic sPS polymer matrix at acidic pH, as reflected by its elevated partition coefficient, further facilitated its interaction with the composite, promoting faster oxidation. In contrast, phenol displayed a lower affinity for the hydrophobic sPS matrix at pH = 2, as evidenced by its lower partition coefficient, allowing it to remain in the liquid phase, reducing over-oxidation and contributing to the higher phenol yield (96 %) observed at acidic pH. This synergistic effect between enhanced hydroxyl radical generation, increased benzene affinity and reduced phenol affinity led to a more efficient photocatalytic process under acidic conditions. These findings establish CuNdT/sPS as a highly efficient, selective, and robust photocatalytic material, combining superior performance, structural stability, and excellent reusability for multiple reaction cycles.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116116"},"PeriodicalIF":6.5,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766523","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1016/j.jcat.2025.116118
Liqun Song , Zhonghai Lin , Zhihua Zhang , Yingcai Fan , Mingwen Zhao
Imine-based covalent organic frameworks (Im-COFs) have attracted extensive attention in photocatalytic Overall Water Splitting (OWS) due to their facile synthesis and structural stability. However, most of the Im-COFs photocatalysts face the challenge of rapid recombination of photogenerated carriers, leading to low Solar-To-Hydrogen (STH) conversion efficiency. Here, we propose that the oxidation of imine to amide linkages in two-dimensional (2D) Im-COFs would be an effective strategy to enhance the in-plane polarity and thus facilitate the separation of photogenerated carriers. Based on first principles calculations, Two amide-linked 2,4,6-triphenyl-1,3,5-triazine (TST) and Triphenylamine (TA) monolayers (Am-TST, Am-TA) were used as model to compare the photocatalytic performance with the imine-linked ones (Im-TST, Im-TA). Interestingly, both the amide-linked COFs exhibit type-II band alignments, which is absent in the imine-linked ones. Moreover, the Non-Adiabatic Molecular Dynamics (NAMD) simulations reveal the photogenerated carriers’ lifetime Am-TST monolayer (13.41 ns) is 3.45 times longer than that of Im-TST monolayer, indicating the superior ability of amide linkages in suppressing the recombination of photoexcited carriers. In addition, the Am-TST monolayer can also achieve visible-light-driven photocatalytic OWS activity, and the light absorption capability can be further improved by using the Am-TST bilayer. These findings reveal the role of imine-to-amide linkages conversion in promoting the separation of photogenerated carriers, providing a promising strategy for designing amide-based COFs photocatalysts towards OWS.
{"title":"Linkages conversion of imine to amide promotes photocatalytic overall water splitting in Two-Dimensional covalent organic frameworks: The role of polarity effects","authors":"Liqun Song , Zhonghai Lin , Zhihua Zhang , Yingcai Fan , Mingwen Zhao","doi":"10.1016/j.jcat.2025.116118","DOIUrl":"10.1016/j.jcat.2025.116118","url":null,"abstract":"<div><div>Imine-based covalent organic frameworks (Im-COFs) have attracted extensive attention in photocatalytic Overall Water Splitting (OWS) due to their facile synthesis and structural stability. However, most of the Im-COFs photocatalysts face the challenge of rapid recombination of photogenerated carriers, leading to low Solar-To-Hydrogen (STH) conversion efficiency. Here, we propose that the oxidation of imine to amide linkages in two-dimensional (2D) Im-COFs would be an effective strategy to enhance the in-plane polarity and thus facilitate the separation of photogenerated carriers. Based on first principles calculations, Two amide-linked 2,4,6-triphenyl-1,3,5-triazine (TST) and Triphenylamine (TA) monolayers (Am-TST, Am-TA) were used as model to compare the photocatalytic performance with the imine-linked ones (Im-TST, Im-TA). Interestingly, both the amide-linked COFs exhibit type-II band alignments, which is absent in the imine-linked ones. Moreover, the Non-Adiabatic Molecular Dynamics (NAMD) simulations reveal the photogenerated carriers’ lifetime Am-TST monolayer (13.41 ns) is 3.45 times longer than that of Im-TST monolayer, indicating the superior ability of amide linkages in suppressing the recombination of photoexcited carriers. In addition, the Am-TST monolayer can also achieve visible-light-driven photocatalytic OWS activity, and the light absorption capability can be further improved by using the Am-TST bilayer. These findings reveal the role of imine-to-amide linkages conversion in promoting the separation of photogenerated carriers, providing a promising strategy for designing amide-based COFs photocatalysts towards OWS.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116118"},"PeriodicalIF":6.5,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143766522","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-03DOI: 10.1016/j.jcat.2025.116102
Ilya V. Chepkasov , Viktor S. Baidyshev , Anastasiia V. Iosimovska , Ivan S. Zamulin , Alexander G. Kvashnin
The great interest in metal nanoparticles is due to the fact that the transition from micro to nano size leads to huge changes in the physical and chemical properties of the material. The local atomic structure and composition can significantly influence the properties of nanoparticles. First-principles calculations are used to study the influence of the structure and chemnical ordering of IrPd nanoparticles on the electronic properties, charge distribution and adsorption energy of O, H, CO, NO, OH. Three different types of PdIr bimetallic nanoparticles with different chemical ordering are considered, namely Pd-core/Ir-shell (Pd@Ir), Ir-core/Pd-shell (Ir@Pd), and bimetallic alloy (Pd-Ir) particles consisting of 79 and 321 atoms with fcc and amorphous structures. The electronic and adsorption properties of the proposed nanoparticles are extensively studied in terms of their ability to adsorb O, H, CO, NO, OH, which opens up the possibility of fine-tuning their properties by modifying the atomic structure and composition. By adjusting the core–shell ratio, the adsorption energy on the nanoparticle surface can be fine-tuned, especially in fcc nanoparticles. This results in a narrower range of adsorption energies, which cannot be achieved with bimetallic alloys. In the case of amorphous nanoparticles, the adsorption energy is highly variable because to there are many non-equivalent adsorption sites on the surface.
{"title":"Adsorption properties of crystalline and amorphous PdIr nanoparticles. A systematic first-principles study","authors":"Ilya V. Chepkasov , Viktor S. Baidyshev , Anastasiia V. Iosimovska , Ivan S. Zamulin , Alexander G. Kvashnin","doi":"10.1016/j.jcat.2025.116102","DOIUrl":"10.1016/j.jcat.2025.116102","url":null,"abstract":"<div><div>The great interest in metal nanoparticles is due to the fact that the transition from micro to nano size leads to huge changes in the physical and chemical properties of the material. The local atomic structure and composition can significantly influence the properties of nanoparticles. First-principles calculations are used to study the influence of the structure and chemnical ordering of IrPd nanoparticles on the electronic properties, charge distribution and adsorption energy of O, H, CO, NO, OH. Three different types of PdIr bimetallic nanoparticles with different chemical ordering are considered, namely Pd-core/Ir-shell (Pd@Ir), Ir-core/Pd-shell (Ir@Pd), and bimetallic alloy (Pd-Ir) particles consisting of 79 and 321 atoms with fcc and amorphous structures. The electronic and adsorption properties of the proposed nanoparticles are extensively studied in terms of their ability to adsorb O, H, CO, NO, OH, which opens up the possibility of fine-tuning their properties by modifying the atomic structure and composition. By adjusting the core–shell ratio, the adsorption energy on the nanoparticle surface can be fine-tuned, especially in fcc nanoparticles. This results in a narrower range of adsorption energies, which cannot be achieved with bimetallic alloys. In the case of amorphous nanoparticles, the adsorption energy is highly variable because to there are many non-equivalent adsorption sites on the surface.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116102"},"PeriodicalIF":6.5,"publicationDate":"2025-04-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.jcat.2025.116120
Xinyu Zhao , Dongxiao Wang , Caiwei Deng , Hao Niu , Huawei Yang , Lixia Yang , Liangjiu Bai , Kun Yin , Donglei Wei , Hou Chen
Photocatalytic aerobic oxidative desulfurization (PAODS) has attracted widespread attention as a sustainable fuel desulfurization method, but the photocatalysts reported so far still suffer from slow sulfide conversion kinetics. Here we propose a MoOx and NiCoP co-decorated on CoNiO2 hollow nanocage (MoOx/P-CoNiO2) catalyst for boosting the PAODS reactions. The photocatalyst exhibits remarkable photocatalytic activity in oxidizing dibenzothiophene (DBT), attaining a mass activity ratio of 10.4 mmol g−1 h−1 and exhibiting excellent repeatability. The strategic incorporation of MoOx and NiCoP as dual cocatalysts significantly improved photocatalytic efficiency by facilitating efficient charge separation, enhancing the production of reactive oxygen species (ROS), and providing active sites for oxidizing refractory sulfur compounds. In real diesel desulfurization tests, the catalyst reduced sulfur content from 559.3 ppm to below 10 ppm, meeting the most stringent transportation diesel standards, highlighting its practical applicability for deep desulfurization in industrial settings.
{"title":"Dual noble-metal-free cocatalysts on cobalt nickel oxide nanocages for boosting photocatalytic oxidation desulfurization","authors":"Xinyu Zhao , Dongxiao Wang , Caiwei Deng , Hao Niu , Huawei Yang , Lixia Yang , Liangjiu Bai , Kun Yin , Donglei Wei , Hou Chen","doi":"10.1016/j.jcat.2025.116120","DOIUrl":"10.1016/j.jcat.2025.116120","url":null,"abstract":"<div><div>Photocatalytic aerobic oxidative desulfurization (PAODS) has attracted widespread attention as a sustainable fuel desulfurization method, but the photocatalysts reported so far still suffer from slow sulfide conversion kinetics. Here we propose a MoO<sub>x</sub> and NiCoP co-decorated on CoNiO<sub>2</sub> hollow nanocage (MoO<sub>x</sub>/P-CoNiO<sub>2</sub>) catalyst for boosting the PAODS reactions. The photocatalyst exhibits remarkable photocatalytic activity in oxidizing dibenzothiophene (DBT), attaining a mass activity ratio of 10.4 mmol g<sup>−1</sup> h<sup>−1</sup> and exhibiting excellent repeatability. The strategic incorporation of MoO<sub>x</sub> and NiCoP as dual cocatalysts significantly improved photocatalytic efficiency by facilitating efficient charge separation, enhancing the production of reactive oxygen species (ROS), and providing active sites for oxidizing refractory sulfur compounds. In real diesel desulfurization tests, the catalyst reduced sulfur content from 559.3 ppm to below 10 ppm, meeting the most stringent transportation diesel standards, highlighting its practical applicability for deep desulfurization in industrial settings.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116120"},"PeriodicalIF":6.5,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758675","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-04-01DOI: 10.1016/j.jcat.2025.116113
Priya Vimal , Babu Rajeev C.P. , Nayela Javeed , Ganga Periyasamy , Gayathri V.
This paper describes the synthesis, characterisation and catalytic transfer hydrogenation reaction of nitro compounds using HCOOH as hydrogen donor and functionalized chloromethylated polystyrene divinylbenzene supported iron complex as catalyst. It was characterized by various analytical techniques such as elemental analysis, ICP-OES, UV–VIS-DRS and FT-IR spectroscopic techniques, EDAX, and thermogravimetric analysis. This supported complex is an efficient catalyst for transfer hydrogenation reaction of aliphatic and aromatic nitro compounds which find application in the synthesis of fine chemicals, API’s and drugs. Interestingly this method has been proven to be tolerant to a broad range of functional groups with good to excellent yields and also established to be superior by exhibiting better catalytic activity and recyclability than the unsupported catalyst. The supported catalyst could be reused seven times without significant loss of catalytic activity. Density functional theory studies shreds light on the possible reaction pathways of transfer hydrogenation reaction catalyzed by Fe(III) system.
{"title":"Synthesis, catalytic application and mechanistic studies of reusable polymer supported iron(III) complex towards efficient transfer hydrogenation of nitro compounds","authors":"Priya Vimal , Babu Rajeev C.P. , Nayela Javeed , Ganga Periyasamy , Gayathri V.","doi":"10.1016/j.jcat.2025.116113","DOIUrl":"10.1016/j.jcat.2025.116113","url":null,"abstract":"<div><div>This paper describes the synthesis, characterisation and catalytic transfer hydrogenation reaction of nitro compounds using HCOOH as hydrogen donor and functionalized chloromethylated polystyrene divinylbenzene supported iron complex as catalyst. It was characterized by various analytical techniques such as elemental analysis, ICP-OES, UV–VIS-DRS and FT-IR spectroscopic techniques, EDAX, and thermogravimetric analysis. This supported complex is an efficient catalyst for transfer hydrogenation reaction of aliphatic and aromatic nitro compounds which find application in the synthesis of fine chemicals, API’s and drugs. Interestingly this method has been proven to be tolerant to a broad range of functional groups with good to excellent yields and also established to be superior by exhibiting better catalytic activity and recyclability than the unsupported catalyst. The supported catalyst could be reused seven times without significant loss of catalytic activity. Density functional theory studies shreds light on the possible reaction pathways of transfer hydrogenation reaction catalyzed by Fe(III) system.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"447 ","pages":"Article 116113"},"PeriodicalIF":6.5,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143758673","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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