Cupric oxide (CuO) is a promising catalyst for CH4 catalytic combustion, but its catalytic oxidation mechanism for CH4 remains unclear. The reaction mechanism of CH4 catalytic oxidation on the CuO surface was investigated using density functional theory calculations based on a periodic CuO (111) surface model. The stepwise oxidation mechanism for CH4 with both O2 and atomic O on the CuO (111) surface model via the Langmuir-Hinshelwood mechanism were studied. The unsaturated Cu top site on the CuO (111) surface model was found to be favorable for CH4 adsorption. The H-abstraction and oxidation of CH4 by adsorbed O2 molecule and atomic O on the CuO (111) surface model were studied. The reaction sequence was identified as CH4* → CH3* → CH3O2* → CH3O* → CH2O* → CHO* → CO* with the H-abstraction of CH4* to produce CH3* identified as the rate-determining step for CH4 oxidation. The reaction activation energy barrier was calculated to be 1.58 eV when reacting with adsorbed O2. The surface adsorbed atomic O could improve the surface catalytic activity towards CH4 oxidation, and the surface adsorbed atomic O could be formed by the OO bond cleavage of CH3O2* and CH2O2*. The coupling of adsorbed CH3 with CH3 and OH forming ethane and methanol on the CuO (111) surface was considered, and the formation of methanol has similar energy barrier compared with the O2 addition to CH3 forming CH3O2. The rate constants for elementary reactions were derived, which helps establish the kinetic model of CH4 oxidation on the CuO (111) surface model.
{"title":"DFT study on the CH4 catalytic combustion on the CuO (111) surface","authors":"Ling-Nan Wu , Jia-Ying Liu , Wu Qin , Zhen-Yu Tian","doi":"10.1016/j.mcat.2026.115752","DOIUrl":"10.1016/j.mcat.2026.115752","url":null,"abstract":"<div><div>Cupric oxide (CuO) is a promising catalyst for CH<sub>4</sub> catalytic combustion, but its catalytic oxidation mechanism for CH<sub>4</sub> remains unclear. The reaction mechanism of CH<sub>4</sub> catalytic oxidation on the CuO surface was investigated using density functional theory calculations based on a periodic CuO (111) surface model. The stepwise oxidation mechanism for CH<sub>4</sub> with both O<sub>2</sub> and atomic O on the CuO (111) surface model via the Langmuir-Hinshelwood mechanism were studied. The unsaturated Cu top site on the CuO (111) surface model was found to be favorable for CH<sub>4</sub> adsorption. The H-abstraction and oxidation of CH<sub>4</sub> by adsorbed O<sub>2</sub> molecule and atomic O on the CuO (111) surface model were studied. The reaction sequence was identified as CH<sub>4</sub>* → CH<sub>3</sub>* → CH<sub>3</sub>O<sub>2</sub>* → CH<sub>3</sub>O* → CH<sub>2</sub>O* → CHO* → CO* with the H-abstraction of CH<sub>4</sub>* to produce CH<sub>3</sub>* identified as the rate-determining step for CH<sub>4</sub> oxidation. The reaction activation energy barrier was calculated to be 1.58 eV when reacting with adsorbed O<sub>2</sub>. The surface adsorbed atomic O could improve the surface catalytic activity towards CH<sub>4</sub> oxidation, and the surface adsorbed atomic O could be formed by the O<img>O bond cleavage of CH<sub>3</sub>O<sub>2</sub>* and CH<sub>2</sub>O<sub>2</sub>*. The coupling of adsorbed CH<sub>3</sub> with CH<sub>3</sub> and OH forming ethane and methanol on the CuO (111) surface was considered, and the formation of methanol has similar energy barrier compared with the O<sub>2</sub> addition to CH<sub>3</sub> forming CH<sub>3</sub>O<sub>2</sub>. The rate constants for elementary reactions were derived, which helps establish the kinetic model of CH<sub>4</sub> oxidation on the CuO (111) surface model.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115752"},"PeriodicalIF":4.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146096105","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 : 2026-02-02DOI: 10.1016/j.mcat.2026.115756
Bo Liu, Jiating Li, Chunyan Xiang, Hongyue Pan, Zemin An, Yuanjie Xu, Lizhi Wu, Li Tan, Yu Tang
The direct conversion of methane into valuable chemicals under mild conditions represents a promising technological pathway, yet achieving both high efficiency and selectivity remains a major challenge in catalysis. In this work, we report a rhodium catalyst atomically dispersed on ZSM-5 for catalytic conversion of methane to oxygenates using H2O2 as oxidant under mild conditions. With carbon monoxide (CO) as a promoter, the catalyst achieved an oxygenates productivity of 46.8 mmol·gcat−1·h−1 (equivalent to 9360 mmol·gRh−1·h−1 or 964.1 mol·molRh−1·h−1) with approximately 90.7 % overall selectivity (including liquid products and gaseous CO2). The catalyst retained high activity over five recycling experiments. A combined investigation by HAADF-STEM, XAFS, and DRIFTS-CO analyses confirms that the active sites consist of atomically dispersed Rh species in a Rh1O5 configuration anchored within the ZSM-5 micropores. Mechanistic studies, including controlled experiments, EPR, and in situ infrared spectroscopy, reveal that CO plays a dual role. It promotes the formation of ·OH radicals from H2O2 and facilitates the activation of methane, leading to the generation of ·CH3 species. Oxygenate products are produced via the direct coupling of ·CH3, ·OH, and CO molecules. This work highlights the potential of tailoring atomically dispersed metal catalysts and using CO as reactant and promoter to enable efficient methane transformation into valuable oxygenates.
{"title":"Efficient and selective oxidation of methane to oxygenates on atomically dispersed Rh catalysts promoted by carbon monoxide","authors":"Bo Liu, Jiating Li, Chunyan Xiang, Hongyue Pan, Zemin An, Yuanjie Xu, Lizhi Wu, Li Tan, Yu Tang","doi":"10.1016/j.mcat.2026.115756","DOIUrl":"10.1016/j.mcat.2026.115756","url":null,"abstract":"<div><div>The direct conversion of methane into valuable chemicals under mild conditions represents a promising technological pathway, yet achieving both high efficiency and selectivity remains a major challenge in catalysis. In this work, we report a rhodium catalyst atomically dispersed on ZSM-5 for catalytic conversion of methane to oxygenates using H<sub>2</sub>O<sub>2</sub> as oxidant under mild conditions. With carbon monoxide (CO) as a promoter, the catalyst achieved an oxygenates productivity of 46.8 mmol·g<sub>cat</sub><sup>−1</sup>·h<sup>−1</sup> (equivalent to 9360 mmol·g<sub>Rh</sub><sup>−1</sup>·h<sup>−1</sup> or 964.1 mol·mol<sub>Rh</sub><sup>−1</sup>·h<sup>−1</sup>) with approximately 90.7 % overall selectivity (including liquid products and gaseous CO<sub>2</sub>). The catalyst retained high activity over five recycling experiments. A combined investigation by HAADF-STEM, XAFS, and DRIFTS-CO analyses confirms that the active sites consist of atomically dispersed Rh species in a Rh<sub>1</sub>O<sub>5</sub> configuration anchored within the ZSM-5 micropores. Mechanistic studies, including controlled experiments, EPR, and <em>in situ</em> infrared spectroscopy, reveal that CO plays a dual role. It promotes the formation of ·OH radicals from H<sub>2</sub>O<sub>2</sub> and facilitates the activation of methane, leading to the generation of ·CH<sub>3</sub> species. Oxygenate products are produced via the direct coupling of ·CH<sub>3</sub>, ·OH, and CO molecules. This work highlights the potential of tailoring atomically dispersed metal catalysts and using CO as reactant and promoter to enable efficient methane transformation into valuable oxygenates.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"593 ","pages":"Article 115756"},"PeriodicalIF":4.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146096097","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.mcat.2026.115766
Boxiang Li , Yan Liu , Jungang Wang , Qiang Wang , Qilong Xie , Wei Zhang , Shupeng Guo , Litao Jia , Congbiao Chen , Zhongyi Ma , Bo Hou , Debao Li
This study clarifies the ambiguous promotional mechanism of ZrO₂ in conventional cobalt-based Fischer-Tropsch synthesis (FTS) catalysts by constructing inverse Co-ZrO₂ model systems. Hexagonal close-packed (HCP) Co nanocrystals with well-defined exposed facets ((10–11), (0001), (11–20)) were synthesized, and ZrO₂ was deposited onto their surfaces to eliminate interference from traditional supports. The optimal catalyst (NMS-Co-4Zr, 10–11) facets with 4wt% Zr) achieves exceptional performance: 93.9% C5+ selectivity with ≤1.7% CH₄ formation at 170 °C, accompanied by robust 240 h stability. Advanced characterizations confirm the formation of Co-Zr interface, where electron transfer from ZrO2 to Co facilitates the dissociation of CO and H₂. Notably, the promotional effect of the Co-Zr interface is universal across different Co facets: it lowers reaction temperatures by 30–110 °C and elevates C5+ selectivity to 85.5–93.9% for all modified catalysts. This work establishes the Co-Zr interface as a structure-independent activity descriptor, providing a paradigm for targeted interfacial engineering in the design of high-efficiency FTS catalysts.
{"title":"Unveiling the role of the Co-Zr interface in Fischer-Tropsch synthesis using inverse Co-ZrO2 catalysts","authors":"Boxiang Li , Yan Liu , Jungang Wang , Qiang Wang , Qilong Xie , Wei Zhang , Shupeng Guo , Litao Jia , Congbiao Chen , Zhongyi Ma , Bo Hou , Debao Li","doi":"10.1016/j.mcat.2026.115766","DOIUrl":"10.1016/j.mcat.2026.115766","url":null,"abstract":"<div><div>This study clarifies the ambiguous promotional mechanism of ZrO₂ in conventional cobalt-based Fischer-Tropsch synthesis (FTS) catalysts by constructing inverse Co-ZrO₂ model systems. Hexagonal close-packed (HCP) Co nanocrystals with well-defined exposed facets ((10–11), (0001), (11–20)) were synthesized, and ZrO₂ was deposited onto their surfaces to eliminate interference from traditional supports. The optimal catalyst (NMS-Co-4Zr, 10–11) facets with 4wt% Zr) achieves exceptional performance: 93.9% C<sub>5</sub><sup>+</sup> selectivity with ≤1.7% CH₄ formation at 170 °C, accompanied by robust 240 h stability. Advanced characterizations confirm the formation of Co-Zr interface, where electron transfer from ZrO<sub>2</sub> to Co facilitates the dissociation of CO and H₂. Notably, the promotional effect of the Co-Zr interface is universal across different Co facets: it lowers reaction temperatures by 30–110 °C and elevates C<sub>5</sub><sup>+</sup> selectivity to 85.5–93.9% for all modified catalysts. This work establishes the Co-Zr interface as a structure-independent activity descriptor, providing a paradigm for targeted interfacial engineering in the design of high-efficiency FTS catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115766"},"PeriodicalIF":4.9,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074334","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-31DOI: 10.1016/j.mcat.2026.115760
Zhihao Wang , Kaiqi Yan , Guanghui Wang , Xiaobo Wang , Shengpeng Xia , Yuyang Fan , Kai Li , Kun Zhao , Zengli Zhao , Anqing Zheng
5-Hydroxymethylfurfural (HMF) is an attractive platform compound derived from lignocellulosic biomass. In order to convert cellulose into HMF in a single pot, a variety of Nb-based metal oxides produced using the co-precipitation-impregnation technique are employed as catalysts. Using 1% Nb2O5-ZrO2-TiO2 (1% Nb-ZrTi) catalysts, an HMF yield of up to 30.9% is achieved at 190 °C for 8 h. Furthermore, the conversion behaviors of potential key intermediates (fructose and glucose) are explored to provide indirect evidence of the complete reaction pathway. To investigate the structure-activity relationship of the Nb-based catalysts, characterization techniques such as pyridine-adsorbed Fourier transform infrared spectrometer (Py-FTIR), ammonia temperature-programmed desorption (NH3-TPD), high-resolution transmission electron microscopy (HR-TEM), and X-ray diffraction (XRD) are employed. It is discovered that the lowest total acid concentration and the lowest Brønsted to Lewis acid sites (B/L) ratios of 1% Nb-ZrTi are associated with its exceptional catalytic activity. Furthermore, after six cycles, the catalyst still demonstrates good recyclability and catalytic activity. These findings give new directions for future catalyst improvement and process development.
{"title":"Catalytic transformation of cellulose into 5-hydroxymethylfurfural by low-loaded Nb-based metal oxide catalysts","authors":"Zhihao Wang , Kaiqi Yan , Guanghui Wang , Xiaobo Wang , Shengpeng Xia , Yuyang Fan , Kai Li , Kun Zhao , Zengli Zhao , Anqing Zheng","doi":"10.1016/j.mcat.2026.115760","DOIUrl":"10.1016/j.mcat.2026.115760","url":null,"abstract":"<div><div>5-Hydroxymethylfurfural (HMF) is an attractive platform compound derived from lignocellulosic biomass. In order to convert cellulose into HMF in a single pot, a variety of Nb-based metal oxides produced using the co-precipitation-impregnation technique are employed as catalysts. Using 1% Nb<sub>2</sub>O<sub>5</sub>-ZrO<sub>2</sub>-TiO<sub>2</sub> (1% Nb-ZrTi) catalysts, an HMF yield of up to 30.9% is achieved at 190 °C for 8 h. Furthermore, the conversion behaviors of potential key intermediates (fructose and glucose) are explored to provide indirect evidence of the complete reaction pathway. To investigate the structure-activity relationship of the Nb-based catalysts, characterization techniques such as pyridine-adsorbed Fourier transform infrared spectrometer (Py-FTIR), ammonia temperature-programmed desorption (NH<sub>3</sub>-TPD), high-resolution transmission electron microscopy (HR-TEM), and X-ray diffraction (XRD) are employed. It is discovered that the lowest total acid concentration and the lowest Brønsted to Lewis acid sites (B/L) ratios of 1% Nb-ZrTi are associated with its exceptional catalytic activity. Furthermore, after six cycles, the catalyst still demonstrates good recyclability and catalytic activity. These findings give new directions for future catalyst improvement and process development.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115760"},"PeriodicalIF":4.9,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074839","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.mcat.2026.115762
Ao Xu, Dan Yu, Jiayuan Gao, Xian Zhao, Haiyang Zhang, Yongchao Lu, Boai Li, Qing Su, Qiaolin Wu
This work reports the construction of two three–component conjugated porous polymers, denoted as NDI-POP and PDI-POP. These polymers incorporate naphthalene diimide (NDI) or perylene diimide (PDI) as acceptor units, with 2–hydroxy–1,3,5–benzenetetracarboxaldehyde (TP) and 2,4,6–trihydroxy–1,3,5–benzenetetracarboxaldehyde (DHTA) serving as donor units. By precisely regulating the donor–acceptor (D-A) synergistic interactions within the conjugated framework, the as–synthesized POPs exhibited a narrower bandgap, strong photocurrent response, and low impedance. Under visible light irradiation and an oxygen (O2) atmosphere, NDI-POP achieves a hydrogen peroxide (H2O2) production rate of 2000 μmol g–1 h–1 in pure water without the involvement of sacrificial reagents, which was 3.39 times of that achieved with the PDI-POP photocatalyst. Photocatalytic cycling experiments further confirm excellent recyclability for both materials. Additionally, controlled experiments verify that efficient H2O2 production proceeds via 2e⁻ oxygen reduction reaction (ORR) pathway. This study provides valuable insights into the regulation of d-A type porous organic materials for enhanced H2O2 generation.
{"title":"D-A type porous organic polymers with NDI/PDI units for efficient photocatalytic H2O2 production","authors":"Ao Xu, Dan Yu, Jiayuan Gao, Xian Zhao, Haiyang Zhang, Yongchao Lu, Boai Li, Qing Su, Qiaolin Wu","doi":"10.1016/j.mcat.2026.115762","DOIUrl":"10.1016/j.mcat.2026.115762","url":null,"abstract":"<div><div>This work reports the construction of two three–component conjugated porous polymers, denoted as NDI-POP and PDI-POP. These polymers incorporate naphthalene diimide (NDI) or perylene diimide (PDI) as acceptor units, with 2–hydroxy–1,3,5–benzenetetracarboxaldehyde (TP) and 2,4,6–trihydroxy–1,3,5–benzenetetracarboxaldehyde (DHTA) serving as donor units. By precisely regulating the donor–acceptor (D-A) synergistic interactions within the conjugated framework, the as–synthesized POPs exhibited a narrower bandgap, strong photocurrent response, and low impedance. Under visible light irradiation and an oxygen (O<sub>2</sub>) atmosphere, NDI-POP achieves a hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) production rate of 2000 μmol g<sup>–1</sup> h<sup>–1</sup> in pure water without the involvement of sacrificial reagents, which was 3.39 times of that achieved with the PDI-POP photocatalyst. Photocatalytic cycling experiments further confirm excellent recyclability for both materials. Additionally, controlled experiments verify that efficient H<sub>2</sub>O<sub>2</sub> production proceeds via 2e⁻ oxygen reduction reaction (ORR) pathway. This study provides valuable insights into the regulation of <span>d</span>-A type porous organic materials for enhanced H<sub>2</sub>O<sub>2</sub> generation.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115762"},"PeriodicalIF":4.9,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074340","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.mcat.2026.115763
Hui-Li Wu , Jia-Wei Liu , Chang-Long Tan , Zi-Rong Tang
Selective photocatalytic dehydrogenation of saturated N-heterocycles represents a sustainable photoredox route for synthesizing valuable nitrogen-containing unsaturated heteroaromatic organics. Herein, we report a Ni-decorated 3D sea urchin-like CdS composite (Ni/CdS) as a dual-functional photocatalyst for the efficient and selective semi-dehydrogenation of 1,2,3,4-tetrahydroisoquinoline (THIQ) to 3,4-dihydroisoquinoline (DHIQ) coupled with H2 evolution under visible light irradiation. The surface-decorated Ni nanoparticles significantly enhance the separation and transfer of photogenerated electron–hole pairs over Ni/CdS, and act as reactive sites for proton reduction to H2, thereby leading to the improved dual-functional photoredox catalysis. Mechanistic studies identify the carbon-centered radical (•CH(NH)C8H8) as a pivotal intermediate in the photocatalytic semi-dehydrogenation of THIQ. This study establishes an effective strategy for designing noble-metal-free photocatalytic systems that integrate selective organic transformations with H2 evolution in a cooperative manner.
{"title":"Dual-functional photoredox catalysis over Ni/CdS composite","authors":"Hui-Li Wu , Jia-Wei Liu , Chang-Long Tan , Zi-Rong Tang","doi":"10.1016/j.mcat.2026.115763","DOIUrl":"10.1016/j.mcat.2026.115763","url":null,"abstract":"<div><div>Selective photocatalytic dehydrogenation of saturated N-heterocycles represents a sustainable photoredox route for synthesizing valuable nitrogen-containing unsaturated heteroaromatic organics. Herein, we report a Ni-decorated 3D sea urchin-like CdS composite (Ni/CdS) as a dual-functional photocatalyst for the efficient and selective semi-dehydrogenation of 1,2,3,4-tetrahydroisoquinoline (THIQ) to 3,4-dihydroisoquinoline (DHIQ) coupled with H<sub>2</sub> evolution under visible light irradiation. The surface-decorated Ni nanoparticles significantly enhance the separation and transfer of photogenerated electron–hole pairs over Ni/CdS, and act as reactive sites for proton reduction to H<sub>2</sub>, thereby leading to the improved dual-functional photoredox catalysis. Mechanistic studies identify the carbon-centered radical (•CH(NH)C<sub>8</sub>H<sub>8</sub>) as a pivotal intermediate in the photocatalytic semi-dehydrogenation of THIQ. This study establishes an effective strategy for designing noble-metal-free photocatalytic systems that integrate selective organic transformations with H<sub>2</sub> evolution in a cooperative manner.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115763"},"PeriodicalIF":4.9,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074841","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.mcat.2026.115753
Shiyi Song , Yajun Wu , Jiacheng Hu , Yuan Hu , Xiaoqing Zhao
To tackle the kinetic constraint of cathode oxygen reactions in energy conversion devices, this study designs high-performance bifunctional ORR/OER electrocatalysts via doping 3d and 4d transition metals into two C3N2 configurations (PC3N2, IC3N2). Single-atom doped IC3N2 displays enhanced stability. For ORR, the ORR overpotential (η) values of Cu-PC3N2, Pd-PC3N2, and Pd-IC3N2 are 0.41, 0.45, and 0.31 V, respectively, indicating that they possess good ORR catalytic activity. For OER, the ηOER values of Pd-PC3N2 and Pd-IC3N2 are 0.21 and 0.53 V respectively, indicating that they possess good OER catalytic potential. For bifunctional catalytic activity, Pd-PC3N2 exhibits the best bifunctional catalytic activity, with a bifunctional index value of only 0.66 V. Moreover, the Random Forest Regression model effectively predicts catalytic performance, achieving an R2 of up to 0.906 and an RMSE of 0.213. This work provides guidance for designing efficient electrocatalysts and highlights machine learning’s utility in catalysis research.
{"title":"Machine learning-assisted improving of C3N2 configurations: transition-metal doped for enhanced bifunctional oxygen electrocatalysis","authors":"Shiyi Song , Yajun Wu , Jiacheng Hu , Yuan Hu , Xiaoqing Zhao","doi":"10.1016/j.mcat.2026.115753","DOIUrl":"10.1016/j.mcat.2026.115753","url":null,"abstract":"<div><div>To tackle the kinetic constraint of cathode oxygen reactions in energy conversion devices, this study designs high-performance bifunctional ORR/OER electrocatalysts via doping 3d and 4d transition metals into two C<sub>3</sub>N<sub>2</sub> configurations (PC<sub>3</sub>N<sub>2</sub>, IC<sub>3</sub>N<sub>2</sub>). Single-atom doped IC<sub>3</sub>N<sub>2</sub> displays enhanced stability. For ORR, the ORR overpotential (<em>η</em>) values of Cu-PC<sub>3</sub>N<sub>2</sub>, Pd-PC<sub>3</sub>N<sub>2</sub>, and Pd-IC<sub>3</sub>N<sub>2</sub> are 0.41, 0.45, and 0.31 V, respectively, indicating that they possess good ORR catalytic activity. For OER, the <em>η</em><sup>OER</sup> values of Pd-PC<sub>3</sub>N<sub>2</sub> and Pd-IC<sub>3</sub>N<sub>2</sub> are 0.21 and 0.53 V respectively, indicating that they possess good OER catalytic potential. For bifunctional catalytic activity, Pd-PC<sub>3</sub>N<sub>2</sub> exhibits the best bifunctional catalytic activity, with a bifunctional index value of only 0.66 V. Moreover, the Random Forest Regression model effectively predicts catalytic performance, achieving an R<sup>2</sup> of up to 0.906 and an RMSE of 0.213. This work provides guidance for designing efficient electrocatalysts and highlights machine learning’s utility in catalysis research.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115753"},"PeriodicalIF":4.9,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.mcat.2026.115751
Li-xin Han , Hong-yue Liu , De-bo Lin , Wen-xian Chen , Gui-lin Zhuang
Using density functional theory (DFT) calculations, this study theoretically designs a new series of two-dimensional (2D) metal-organic framework-based catalysts (TMn@PGI-MOF) (Ru1-3, Rh1-3, Pd1-3, Ag1-3, Os1-3, Ir1-3, Pt1-3, Au1-3) incorporating single-cluster catalysts (SCCs) of precious metals into specific phenyl-isocyanide nodes. DFT calculations reveal that several TMn@PGI-MOF structures are active for the oxygen reduction reaction (ORR). In terms of thermodynamics: TMn@PGI-MOF (Pd1-2) are selective for the 4e⁻ ORR pathway with overpotentials (η) of 0.35 V and 0.26 V, respectively. In contrast, TMn@PGI-MOF (Pd1, Ag2, Au2) are highly selective for the 2e⁻ ORR pathway, among which Pd1@PGI-MOF has ηORR = 0.18 V, while Ag2@PGI-MOF and Au2@PGI-MOF show particularly low ηORR = 0.08 V and 0.09 V, respectively. Under constant potential conditions, the onset potentials for the ORR reveal distinct catalytic pathways. For the 4e⁻ ORR pathway, at pH = 1, TMn@PGI-MOF (Pd1-2) have onset potentials of 0.98 V/RHE and 0.76 V/RHE, respectively, while at pH = 13, Pd1@PGI-MOF exhibits an onset potential of 0.40 V/RHE. For the 2e⁻ ORR pathway, TMn@PGI-MOF (Pd1-2, Ag2, Au2) all exhibit extremely low onset potentials. This work demonstrates that incorporating atomically precise metal clusters into 2D PGI-MOF is a powerful strategy for designing selective ORR electrocatalysts.
{"title":"Electrocatalytic oxygen reduction reaction on single-cluster catalyst in 2D metal-organic frameworks: A density functional theory study","authors":"Li-xin Han , Hong-yue Liu , De-bo Lin , Wen-xian Chen , Gui-lin Zhuang","doi":"10.1016/j.mcat.2026.115751","DOIUrl":"10.1016/j.mcat.2026.115751","url":null,"abstract":"<div><div>Using density functional theory (DFT) calculations, this study theoretically designs a new series of two-dimensional (2D) metal-organic framework-based catalysts (TM<em><sub>n</sub></em>@PGI-MOF) (Ru<sub>1-3</sub>, Rh<sub>1-3</sub>, Pd<sub>1-3</sub>, Ag<sub>1-3</sub>, Os<sub>1-3</sub>, Ir<sub>1-3</sub>, Pt<sub>1-3</sub>, Au<sub>1-3</sub>) incorporating single-cluster catalysts (SCCs) of precious metals into specific phenyl-isocyanide nodes. DFT calculations reveal that several TM<em><sub>n</sub></em>@PGI-MOF structures are active for the oxygen reduction reaction (ORR). In terms of thermodynamics: TM<em><sub>n</sub></em>@PGI-MOF (Pd<sub>1-2</sub>) are selective for the 4e⁻ ORR pathway with overpotentials (<em>η</em>) of 0.35 V and 0.26 V, respectively. In contrast, TM<em><sub>n</sub></em>@PGI-MOF (Pd<sub>1</sub>, Ag<sub>2</sub>, Au<sub>2</sub>) are highly selective for the 2e⁻ ORR pathway, among which Pd<sub>1</sub>@PGI-MOF has <em>η</em><sup>ORR</sup> = 0.18 V, while Ag<sub>2</sub>@PGI-MOF and Au<sub>2</sub>@PGI-MOF show particularly low <em>η</em><sup>ORR</sup> = 0.08 V and 0.09 V, respectively. Under constant potential conditions, the onset potentials for the ORR reveal distinct catalytic pathways. For the 4e⁻ ORR pathway, at pH = 1, TM<em><sub>n</sub></em>@PGI-MOF (Pd<sub>1-2</sub>) have onset potentials of 0.98 V/RHE and 0.76 V/RHE, respectively, while at pH = 13, Pd<sub>1</sub>@PGI-MOF exhibits an onset potential of 0.40 V/RHE. For the 2e⁻ ORR pathway, TM<em><sub>n</sub></em>@PGI-MOF (Pd<sub>1-2</sub>, Ag<sub>2</sub>, Au<sub>2</sub>) all exhibit extremely low onset potentials. This work demonstrates that incorporating atomically precise metal clusters into 2D PGI-MOF is a powerful strategy for designing selective ORR electrocatalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115751"},"PeriodicalIF":4.9,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074415","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.mcat.2026.115757
Yun-Rui Lv , Jia-Hui Zhang , Kun Fang , Duo-Duo Liu , Nan Li , Li-Ping Si , Hai-Yang Liu
Achieving low-cost and scalable fabrication of oxygen reduction reaction (ORR) catalysts remains one of the central challenges for the commercialization of high-performance energy conversion devices. In this work, Livistona chinensis leaves (LCL) are used as the sustainable bioorganic frame (BOF) precursor for constructing the carbon material LCLC. After doping transition metal (Fe, Co, Mn) 1, 10, 15-tris(pentafluorophenyl)corrole (TPFC) complexes and followed by pyrolysis, the carbon based ORR electrocatalysts MTPFC/LCLC bearing the metal-nitrogen-carbon (M-N-C) active site were prepared. Of all prepared MTPFC/LCLC, the iron corrole doped carbon material FeTPFC/LCLC exhibited the best electrocatalytic ORR activity, featuring a half-wave potential (E1/2) of 0.877 V (Vs the reversible hydrogen electrode, RHE). The constructed zinc-air battery (ZAB) by using FeTPFC/LCLC cathode achieved an open-circuit voltage of 1.48 V and a specific capacity of 809.9 mAh g-1 (based on consumed Zn), both surpassing the commercial Pt/C catalyst. Our work proved the tremendous potential of Bioorganic frame derived carbon and metal corrolates for practical ORR catalysts.
实现低成本和可扩展的氧还原反应（ORR）催化剂的制造仍然是高性能能量转换设备商业化的核心挑战之一。本研究以中国紫菜叶片（LCL）作为构建碳材料LCLC的可持续生物有机骨架（BOF）前体。通过掺杂过渡金属（Fe, Co, Mn） 1,10,15 -三（五氟苯基）corole （TPFC）配合物并进行热解，制备了具有金属-氮-碳（M-N-C）活性位的碳基ORR电催化剂MTPFC/LCLC。在所有制备的MTPFC/LCLC中，铁掺杂碳材料FeTPFC/LCLC表现出最好的电催化ORR活性，其半波电位（E1/2）为0.877 V （Vs可逆氢电极，RHE）。采用fepfc /LCLC阴极构建的锌空气电池（ZAB）开路电压为1.48 V，比容量为809.9 mAh g-1（基于消耗的Zn），均超过了商用Pt/C催化剂。我们的工作证明了生物有机框架衍生的碳和金属衍生物作为实际ORR催化剂的巨大潜力。
{"title":"Livistona Chinensis leaf as bioorganic frame for porous carbon support and metal corrolate as M-N-C active site to construct oxygen reduction reaction electrocatalyst","authors":"Yun-Rui Lv , Jia-Hui Zhang , Kun Fang , Duo-Duo Liu , Nan Li , Li-Ping Si , Hai-Yang Liu","doi":"10.1016/j.mcat.2026.115757","DOIUrl":"10.1016/j.mcat.2026.115757","url":null,"abstract":"<div><div>Achieving low-cost and scalable fabrication of oxygen reduction reaction (ORR) catalysts remains one of the central challenges for the commercialization of high-performance energy conversion devices. In this work, <em>Livistona chinensis</em> leaves (LCL) are used as the sustainable bioorganic frame (BOF) precursor for constructing the carbon material LCLC. After doping transition metal (Fe, Co, Mn) 1, 10, 15-tris(pentafluorophenyl)corrole (TPFC) complexes and followed by pyrolysis, the carbon based ORR electrocatalysts MTPFC/LCLC bearing the metal-nitrogen-carbon (M-N-C) active site were prepared. Of all prepared MTPFC/LCLC, the iron corrole doped carbon material FeTPFC/LCLC exhibited the best electrocatalytic ORR activity, featuring a half-wave potential (<em>E</em><sub>1/2</sub>) of 0.877 V (Vs the reversible hydrogen electrode, RHE). The constructed zinc-air battery (ZAB) by using FeTPFC/LCLC cathode achieved an open-circuit voltage of 1.48 V and a specific capacity of 809.9 mAh g<sup>-1</sup> (based on consumed Zn), both surpassing the commercial Pt/C catalyst. Our work proved the tremendous potential of Bioorganic frame derived carbon and metal corrolates for practical ORR catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115757"},"PeriodicalIF":4.9,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074414","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-30DOI: 10.1016/j.mcat.2026.115755
Redae Nuguse Berhe , Martha Dagnew , Juwon Park , Joon Wun Kang , Hyunook Kim
Recent research has been focused on synthesizing iron oxide (Fe3O4) nanoparticles (Fe3O4 NPs) for wastewater treatment via electrochemical oxidation. In this study, Fe3O4 NPs of various sizes were synthesized from iron chloride salts (Fe3O4 NPs-C), iron sulfate salts (Fe3O4 NPs-S) and a mixture of both salts (Fe3O4 NPs-M). The effect of pH and anionic strength of each salt precursor on the size distribution of Fe3O4 NPs (C, S, and M) was investigated. The synthesized Fe3O4 NPs were characterized using several techniques to analyze their physio-chemical properties. Field emission-scanning electron microscope (FE-SEM) and vibrating sample magnetometer analysis of Fe3O4 NPs (C, S, and M) revealed average hydrodynamic diameter of 23, 17 and 48 nm, with saturation magnetization of 76 ± 2.4, 79 ± 2.6 and 66 ± 2.8 emu g-1, respectively. Dispersed Fe3O4 NPs were prepared from each Fe3O4 NPs (C, S, and M), achieving catalytic oxidation efficiencies for Acid Orange 7 (AO7) of 89.4 ± 1.7%, 93.2 ± 1.5% and 83.7 ± 2.3%, respectively. At optimal operating conditions, 97.8 ± 1.4% oxidation efficiency was obtained over 40 min using Fe3O4 NPs-S heterogenous electrode. Finally, the regeneration efficiency of Fe3O4 NPs-S was found to be 54.3 ± 2.8% after seven consecutive cycles, demonstrating the potential of these synthesized heterogenous dispersed Fe3O4 NPs for efficient and reusable electrocatalytic oxidation of organic pollutants.
{"title":"Synthesis of iron nanoparticles for heterogeneous electrocatalytic oxidation of acid orange dye: In situ and stepwise mechanism","authors":"Redae Nuguse Berhe , Martha Dagnew , Juwon Park , Joon Wun Kang , Hyunook Kim","doi":"10.1016/j.mcat.2026.115755","DOIUrl":"10.1016/j.mcat.2026.115755","url":null,"abstract":"<div><div>Recent research has been focused on synthesizing iron oxide (Fe<sub>3</sub>O<sub>4</sub>) nanoparticles (Fe<sub>3</sub>O<sub>4</sub> NPs) for wastewater treatment via electrochemical oxidation. In this study, Fe<sub>3</sub>O<sub>4</sub> NPs of various sizes were synthesized from iron chloride salts (Fe<sub>3</sub>O<sub>4</sub> NPs-C), iron sulfate salts (Fe<sub>3</sub>O<sub>4</sub> NPs-S) and a mixture of both salts (Fe<sub>3</sub>O<sub>4</sub> NPs-M). The effect of pH and anionic strength of each salt precursor on the size distribution of Fe<sub>3</sub>O<sub>4</sub> NPs (C, S, and M) was investigated. The synthesized Fe<sub>3</sub>O<sub>4</sub> NPs were characterized using several techniques to analyze their physio-chemical properties. Field emission-scanning electron microscope (FE-SEM) and vibrating sample magnetometer analysis of Fe<sub>3</sub>O<sub>4</sub> NPs (C, S, and M) revealed average hydrodynamic diameter of 23, 17 and 48 nm, with saturation magnetization of 76 ± 2.4, 79 ± 2.6 and 66 ± 2.8 emu g<sup>-1</sup>, respectively. Dispersed Fe<sub>3</sub>O<sub>4</sub> NPs were prepared from each Fe<sub>3</sub>O<sub>4</sub> NPs (C, S, and M), achieving catalytic oxidation efficiencies for Acid Orange 7 (AO7) of 89.4 ± 1.7%, 93.2 ± 1.5% and 83.7 ± 2.3%, respectively. At optimal operating conditions, 97.8 ± 1.4% oxidation efficiency was obtained over 40 min using Fe<sub>3</sub>O<sub>4</sub> NPs-S heterogenous electrode. Finally, the regeneration efficiency of Fe<sub>3</sub>O<sub>4</sub> NPs-S was found to be 54.3 ± 2.8% after seven consecutive cycles, demonstrating the potential of these synthesized heterogenous dispersed Fe<sub>3</sub>O<sub>4</sub> NPs for efficient and reusable electrocatalytic oxidation of organic pollutants.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"592 ","pages":"Article 115755"},"PeriodicalIF":4.9,"publicationDate":"2026-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146074335","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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