Molecular Catalysis最新文献

英文中文

A green strategy for CO2 cycloaddition: adjusting the charge distribution on MgO leads to mechanism reversal

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-10 DOI: 10.1016/j.mcat.2025.115105

Yunya Guo , Jiexun Zheng , Shuqi Wang , Zilong Wang , Lixia Ling , Riguang Zhang , Heqin Guo , Debao Li , Baojun Wang

The CO₂ cycloaddition with ethylene oxide (EO) to generate ethylene carbonate (EC) is a green method for converting exhaust gas into fine chemicals. However, pure MgO exhibits low EC yield under halogen-free and mild reaction conditions. This study explores EC generation on single-atom catalysts of MgO(100) surfaces loaded with Cu, Ag, Au, Zn, Na, K, Ca, Sr, Ba, Al, Ga and In through density functional theory (DFT) calculation. The results show that the mechanism reversal observed in the reaction pathway for EC generation and the role of CO₂ are attributed to changes in the electrons number obtained by EO and CO₂ co-adsorbed on the MgO(100) surfaces loaded with metals. For EC generation, surfaces loaded with Cu, Ag, Au, and Zn show a synergistic route where EO and CO₂ obtained fewer than 0.50 |e|. However, other surfaces have a stepwise pathway when this number exceeds 0.50. The participation of CO₂'s frontier orbitals in the reaction depends on the electrons obtained from the catalyst. On the Cu, Ag, Au, Zn, Na, and K-MgO(100) surfaces, CO₂ obtains fewer than 0.50 |e| and contributes LUMO orbitals, whereas on other surfaces, it obtains >0.50 |e| and contributes HOMO orbitals. Notably, the Cu-MgO(100) surface exhibits over 98 % EC selectivity at 1 atm and 298 K due to its weak alkalinity. It provides an ideal microenvironment that activates EO and CO₂, replacing the role of halogens and offering a novel catalyst to significantly boost EC yield under halogen-free and mild reaction conditions.

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引用次数: 0

Synthesis of cobalt sulfide–NC composite catalyst assisted by polyaniline as nonprecious electrocatalyst for oxygen reduction reaction

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-10 DOI: 10.1016/j.mcat.2025.115107

Jae Sang Lee , Won Suk Jung

The scarce, expensive Pt is the preferred catalyst for the oxygen reduction reaction (ORR) in metal–air batteries or fuel cells. In this study, a composite catalyst consisting of cobalt sulfide and polyaniline (PANI) was utilized for optimal ORR kinetics. Cobalt sulfide catalysts were prepared at different temperatures, the optimal cobalt sulfide catalyst was coated with PANI, and the coated catalyst was annealed to form a core–shell cobalt sulfide@NC composite catalyst. Structural characterization was performed via X-ray diffraction (XRD) and Raman spectroscopy, scanning electron microscopy, and high-resolution transmission electron microscopy (HR-TEM) were conducted to characterize the catalyst morphology. CoS-160 exhibited a flower-like structure; CoS-180, containing Co₉S₈, exhibited both flower-like and sheet structures; and CoS-200 exhibited a sheet structure. With an increase in temperature, XRD and Raman spectroscopy verified the formation of Co₉S₈, serving as ORR active sites, in CoS-180 and CoS-200. HR-TEM indicated that the Co₉S₈-x@NC catalysts had a core–shell structure. Among them, Co₉S₈–180@NC had the highest graphitization degree, and total nitrogen, pyridinic N, graphitic N contents, resulting in the highest onset potential, limiting current density and the lowest Tafel slope for ORR in alkaline media among the catalysts. In an accelerated stress test, a performance degradation of less than 1 % was observed, and a chronoamperometry test demonstrated a current retention rate of 95.49 %.

稀缺而昂贵的铂是金属空气电池或燃料电池中氧还原反应（ORR）的首选催化剂。本研究利用硫化钴和聚苯胺（PANI）组成的复合催化剂来优化 ORR 动力学。硫化钴催化剂在不同温度下制备，最佳硫化钴催化剂涂覆 PANI，涂覆催化剂退火形成核壳硫化钴@NC 复合催化剂。通过 X 射线衍射（XRD）和拉曼光谱进行了结构表征，扫描电子显微镜和高分辨率透射电子显微镜（HR-TEM）对催化剂形态进行了表征。CoS-160 呈现花状结构；含有 Co9S8 的 CoS-180 同时呈现花状和片状结构；CoS-200 则呈现片状结构。随着温度的升高，XRD 和拉曼光谱验证了 CoS-180 和 CoS-200 中作为 ORR 活性位点的 Co9S8 的形成。HR-TEM 表明 Co9S8-x@NC 催化剂具有核壳结构。其中，Co9S8-180@NC 的石墨化程度、总氮、吡啶 N、石墨 N 含量最高，因此在碱性介质中的 ORR 起始电位、极限电流密度最高，Tafel 斜率最低。在加速应力测试中，观察到的性能衰减小于 1%，而计时器测试显示的电流保持率为 95.49%。

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引用次数: 0

Visible-light-induced C–S bond formation of pyrazolin-5-ones with thioureas to pyrazol-4-yl carbamimidothioates 可见光诱导吡唑啉-5-酮与硫脲形成 C-S 键，生成吡唑-4-基硫代氨基甲酰亚胺酸盐

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-07 DOI: 10.1016/j.mcat.2025.115086

Renhua Zheng , Haichang Guo , Xiurong Hu , Lei Wang

A simple, highly efficient and environmentally benign method for the synthesis of pyrazol-4-yl carbamimidothioates was reported. Under visible light irradiation and Eosin Y as photocatalyst, a variety of pyrazol-4-yl carbamimidothioates were obtained in good to excellent yields via C–S bond formation of pyrazolin-5-ones with thioureas in ethanol. The protocol features the advantages of easy performance, environmental friendliness, high yields, and good functional tolerance, showing potential value for the preparation of some biologically active compounds.

本研究报道了一种简单、高效且对环境无害的合成吡唑-4-基硫代氨基甲酰亚胺的方法。在可见光照射下，以 Eosin Y 为光催化剂，通过吡唑啉-5-酮与硫脲类化合物在乙醇中形成 C-S 键，获得了多种吡唑-4-基硫代氨基甲酰亚胺，收率从良好到极佳。该方法具有操作简便、环境友好、产率高、功能耐受性好等优点，对制备一些具有生物活性的化合物具有潜在价值。

引用次数: 0

The cascade catalysis of core-shell CoW-MOF: Further intensified allylic oxidation of cyclohexene to 2-cyclohexene-1-one

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-07 DOI: 10.1016/j.mcat.2025.115098

Peng Dong , Tingna Shao , Jiangpeng Xie , Xiaohui Zhang , Yang Xin , Xiaorui Wang , Yu Zhao , Guixian Li

The low selectivity of cyclohexene allylic oxidation products (2-cyclohexene-1-one and 2-cyclohexene-1-ol) is the main barrier hindering the industrialization process of the cyclohexene allylic oxidation reaction. Improving the selectivity of 2-cyclohexene-1-one through cascade catalysis is an innovative strategy for the preparation of a single-target product from cyclohexene. In this paper, based on the “dissolution-regeneration” process, the Co-based metal-organic framework ZIF-67 was reconstructed using Na₂WO₄·4H₂O (as the W sources). a series of core-shell nanostructured catalysts (Co_xW_y-MOF) composed of a ZIF-67 core and a CoWO₄ shell layer were obtained. These catalysts have a specific surface area one order of magnitude higher than that of the porous CoWO₄ composite oxide. Thus, the significantly abundant active Co and W sites were evenly dispersed on such a high specific surface area for the cyclohexene allylic cascade reaction to generate 2-cyclohexene-1-one. Compared with porous CoWO₄ composite oxide, the conversion rate of Co_0.5W_0.5-MOF catalyst to cyclohexene increased by 9.8 %, and the value was 87.6 %. The selectivity for 2-cyclohexene-1-one is increased by 12.5 %, and the value was 83.3 %. Moreover, it can maintain its catalytic performance after five catalytic cycles of repeated use. The reasons for further intensified the cyclohexene allylic cascade oxidation mechanism are the full exposure of the active sites in the CoWO₄ shell layer and the synergistic catalytic effect between the ZIF-67 core and the CoWO₄ shell layer. The new material of CoWO₄ surface reconstruction based on the ZIF-67 precursor is an efficient catalyst for the cyclohexene allylic oxidation to produce 2-cyclohexene-1-one.

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引用次数: 0

One-pot hydroformylation/hydrogenation of bio-renewable (R)-carvone in a recyclable Rh-catalyzed aqueous biphasic medium: Targeting dual remote sites with a single catalyst

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-07 DOI: 10.1016/j.mcat.2025.115102

Rupali S. Prajapati, Bhalchandra M. Bhanage

A potent methodology was designed for the one-pot hydroformylation/hydrogenation of the biomass-based olefin, (R)-carvone in an aqueous biphasic medium, regiospecifically producing the corresponding linear aldehyde as the desired product. The protocol was made more sustainable as a result of, the reusability of the catalytic system, the use of water as an eco-solvent, the employment of affordable ligand and phase transfer agent. Moreover, only a single Rh-based catalyst was applied for executing distinct reactions at two different remote sites of the substrate. Selectivity tuning of the system with respect to temperature, pressure, concentration of cetyltrimethylammonium bromide (CTAB), catalyst to ligand ratio, kinds of phase transfer agents, aqueous phase volume, reaction time and catalyst to substrate ratio furnished a high chemoselectivity of 97 %, along with a full conversion. The catalytic system could be recycled for at least four consecutive cycles without a significant loss in the activity.

引用次数: 0

Continuous-flow chemoenzymatic conversion of racemic alcohols to enantiopure alcohols and amines

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-07 DOI: 10.1016/j.mcat.2025.115094

Jiali Chen , Chen Huang , Yuqing Zhang , Liya Zhou , Li Ma , Lihui Wang , Yanjun Jiang , Yunting Liu

The conversion of racemic alcohols to enantiopure alcohols and amines is of significant importance yet presents considerable challenges. Herein, we achieved this goal by developing continuous-flow chemoenzymatic systems. In chemical module, a ruthenium (II)-N-heterocyclic carbene (Ru-NHC) catalyst immobilized on dendritic organosilica nanoparticle (DON) was prepared, which exhibited high activity and selectivity in the dehydrogenative oxidation of racemic alcohols to ketones. In enzymatic module, a ketoreductase and an amine dehydrogenase were individually co-immobilized with a cofactor-regenerating enzyme (glucose dehydrogenase) on DON for the enantioselective conversion of ketones to chiral alcohols and amines, respectively. The integration of the two modules in continuous-flow systems enabled the efficient chemoenzymatic deracemization and asymmetric amination of racemic alcohols (9 examples) with the maximum space-time yields of 6.8 and 5.8 g L^-1 h^-1, respectively, underscoring the practical utility of the continuous-flow chemoenzymatic systems.

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引用次数: 0

Promoting distribution of surface-active sites by regulates interfacial binding of TiO2 and Pt using organic acid: stable Cl-VOCs catalytic properties

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-05 DOI: 10.1016/j.mcat.2025.115077

Esimoneze Emmanuel Chinedu , Dilong Qiang , Xueqian Wu , Wei Liu , Haizhou Cao , Zhaolian Ye , Zhen Li , Songjian Zhao

The Pt-based catalyst for purifying chlorinated volatile organic compounds (Cl-VOCs) has the advantages of high catalytic efficiency and low ignition temperature, but the problem of poor resistance to chlorine and water poisoning has not been effectively solved. A series of 0.5 Pt-Ti catalysts were prepared for chlorobenzene (CB) catalytic oxidation by adjusting the interfacial stability and dispersibility of the TiO₂ and Pt through the organic acid strategy in this study. The introduction of tartaric acid (TA) effectively enhanced the surface reduction performance of 0.5Pt-Ti-TA and the proportion of Pt⁴⁺ on the surface. In addition, TA can strongly coordinate with Ti center to form stable titanium-containing complexes, improve the dispersion of Pt, prevent particles from agglomerating, and make the distribution of active sites more uniform. The designed 0.5Pt-Ti-TA exhibits excellent chlorine and water resistance at 300℃ (5 %H₂O, 500 ppm CB), and has a higher potential of application.

用于净化氯化挥发性有机化合物（Cl-VOCs）的铂基催化剂具有催化效率高、着火温度低等优点，但其抗氯气和水毒性差的问题一直未得到有效解决。本研究通过有机酸策略调节 TiO2 和 Pt 的界面稳定性和分散性，制备了一系列 0.5 Pt-Ti 催化剂，用于氯苯（CB）催化氧化。酒石酸（TA）的引入有效提高了 0.5Pt-Ti-TA 的表面还原性能和表面 Pt4+ 的比例。此外，TA 能与 Ti 中心强配位，形成稳定的含钛络合物，改善铂的分散性，防止颗粒团聚，使活性位点分布更均匀。所设计的 0.5Pt-Ti-TA 在 300℃（5%H2O，500 ppm CB）条件下表现出优异的耐氯性和耐水性，具有更高的应用潜力。

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引用次数: 0

Electronic properties and photocatalytic characteristics with high solar-to-hydrogen efficiency in a promising S-scheme Hf2CO2/SiS2 heterojunction: First-principles calculations

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-05 DOI: 10.1016/j.mcat.2025.115096

Dahai Yu, Qingquan Xiao, Jianfeng Ye, Shengshang Lu, Songguo Yu, Fuqiang Ai

The structural, electronic, and optical properties of the Hf₂CO₂/SiS₂ heterojunction were analyzed using first-principles calculations, and the effects of biaxial strains on its band structure and optical absorption were also investigated. The results show that the Hf₂CO₂/SiS₂ heterojunction exhibits an indirect bandgap of 1.05 eV and non-trivial band overlap, which facilitates efficient charge separation and transport. Differential charge density analysis reveals charge transfer at the interface, forming an intrinsic electric field that enhances the separation of photogenerated carriers and thereby improves photocatalytic performance. The Hf₂CO₂/SiS₂ heterojunction aligns with the S-scheme heterojunction model, enabling effective separation of photogenerated electron-hole pairs. Optical analysis shows significant light absorption in the UV and visible regions, with a redshift compared to monolayer materials. The predicted solar-to-hydrogen (STH) conversion efficiency of the Hf₂CO₂/SiS₂ heterojunction reaches 55.20 %, highlighting its potential for photocatalytic hydrogen production. Surface modification through elemental doping optimizes hydrogen evolution reaction (HER) activity of the Hf₂CO₂/SiS₂ heterojunction, ensuring exothermic reactions. Under alkaline conditions, the oxygen evolution reaction (OER) process of the Hf₂CO₂/SiS₂ heterojunction is spontaneous. Biaxial strain tuning further optimizes the bandgap and optical absorption properties of the Hf₂CO₂/SiS₂ heterojunction, thereby enhancing its photocatalytic performance. The research provides highly potential candidate materials for exploring efficient hydrogen evolution catalysts.

{"title":"Electronic properties and photocatalytic characteristics with high solar-to-hydrogen efficiency in a promising S-scheme Hf2CO2/SiS2 heterojunction: First-principles calculations","authors":"Dahai Yu, Qingquan Xiao, Jianfeng Ye, Shengshang Lu, Songguo Yu, Fuqiang Ai","doi":"10.1016/j.mcat.2025.115096","DOIUrl":"10.1016/j.mcat.2025.115096","url":null,"abstract":"<div><div>The structural, electronic, and optical properties of the Hf<sub>2</sub>CO<sub>2</sub>/SiS<sub>2</sub> heterojunction were analyzed using first-principles calculations, and the effects of biaxial strains on its band structure and optical absorption were also investigated. The results show that the Hf<sub>2</sub>CO<sub>2</sub>/SiS<sub>2</sub> heterojunction exhibits an indirect bandgap of 1.05 eV and non-trivial band overlap, which facilitates efficient charge separation and transport. Differential charge density analysis reveals charge transfer at the interface, forming an intrinsic electric field that enhances the separation of photogenerated carriers and thereby improves photocatalytic performance. The Hf<sub>2</sub>CO<sub>2</sub>/SiS<sub>2</sub> heterojunction aligns with the S-scheme heterojunction model, enabling effective separation of photogenerated electron-hole pairs. Optical analysis shows significant light absorption in the UV and visible regions, with a redshift compared to monolayer materials. The predicted solar-to-hydrogen (STH) conversion efficiency of the Hf<sub>2</sub>CO<sub>2</sub>/SiS<sub>2</sub> heterojunction reaches 55.20 %, highlighting its potential for photocatalytic hydrogen production. Surface modification through elemental doping optimizes hydrogen evolution reaction (HER) activity of the Hf<sub>2</sub>CO<sub>2</sub>/SiS<sub>2</sub> heterojunction, ensuring exothermic reactions. Under alkaline conditions, the oxygen evolution reaction (OER) process of the Hf<sub>2</sub>CO<sub>2</sub>/SiS<sub>2</sub> heterojunction is spontaneous. Biaxial strain tuning further optimizes the bandgap and optical absorption properties of the Hf<sub>2</sub>CO<sub>2</sub>/SiS<sub>2</sub> heterojunction, thereby enhancing its photocatalytic performance. The research provides highly potential candidate materials for exploring efficient hydrogen evolution catalysts.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115096"},"PeriodicalIF":3.9,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776979","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}

引用次数: 0

Exchanged oxo-Cu2+ cations in mordenite zeolites: Evidencing the truly active in the stepwise conversion of methane to methanol from in situ DRS-UV–vis analyses performed during activation and reaction

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-05 DOI: 10.1016/j.mcat.2025.115093

Monize Picinini , Mateus Gonçalves dos Santos , José Maria C. Bueno , Ernesto A. Urquieta-Gonzalez

After activation, Cu²⁺-exchanged zeolites generate exchanged oxo-Cu²⁺ cations that absorb UV–vis radiation in all of the d-d and LMCT transitions range. On the other hand, based on great experimental and/or theoretical data, bi- or trinuclear exchanged oxo-Cu²⁺-zeolites with attributed absorption UV–vis bands centered between 20,000 and 35,000 cm^-1, are the mainly considered as the potential active species to directly convert methane to methanol (MTM) in a stepwise process, which obviously leads to low copper specific activities (TON). What about the others generated oxo-Cu²⁺ cations? To elucidate this question, we developed a systematic study using catalytic evaluation data of oxo-Cu²⁺ mordenites and in situ DRS-UV–vis analyses performed during air activation at 550 °C and MTM conversion at 200 °C. The obtained data allowed to confirm that the less-generated oxo-Cu²⁺ cations related to absorption DRS-UV–vis bands centered at wavenumbers lower than 33,000 cm^-1, are the effectively active species to directly oxidize the methane molecule to methanol, but also evidencing that the most generated oxo-Cu²⁺ cations are poorly active, thus explaining the reported low copper TON values of activated Cu²⁺-exchanged zeolites. This finding must stimulate the involved scientific community to find more effective activation procedures that can promote the formation of such more active oxo-Cu²⁺ cations.

{"title":"Exchanged oxo-Cu2+ cations in mordenite zeolites: Evidencing the truly active in the stepwise conversion of methane to methanol from in situ DRS-UV–vis analyses performed during activation and reaction","authors":"Monize Picinini , Mateus Gonçalves dos Santos , José Maria C. Bueno , Ernesto A. Urquieta-Gonzalez","doi":"10.1016/j.mcat.2025.115093","DOIUrl":"10.1016/j.mcat.2025.115093","url":null,"abstract":"<div><div>After activation, Cu<sup>2+</sup>-exchanged zeolites generate exchanged oxo-Cu<sup>2+</sup> cations that absorb UV–vis radiation in all of the d-d and LMCT transitions range. On the other hand, based on great experimental and/or theoretical data, bi- or trinuclear exchanged oxo-Cu<sup>2+</sup>-zeolites with attributed absorption UV–vis bands centered between 20,000 and 35,000 cm<sup>-1</sup>, are the mainly considered as the potential active species to directly convert methane to methanol (MTM) in a stepwise process, which obviously leads to low copper specific activities (TON). What about the others generated oxo-Cu<sup>2+</sup> cations? To elucidate this question, we developed a systematic study using catalytic evaluation data of oxo-Cu<sup>2+</sup> mordenites and <em>in situ</em> DRS-UV–vis analyses performed during air activation at 550 °C and MTM conversion at 200 °C. The obtained data allowed to confirm that the less-generated oxo-Cu<sup>2+</sup> cations related to absorption DRS-UV–vis bands centered at wavenumbers lower than 33,000 cm<sup>-1</sup>, are the effectively active species to directly oxidize the methane molecule to methanol, but also evidencing that the most generated oxo-Cu<sup>2+</sup> cations are poorly active, thus explaining the reported low copper TON values of activated Cu<sup>2+</sup>-exchanged zeolites. This finding must stimulate the involved scientific community to find more effective activation procedures that can promote the formation of such more active oxo-Cu<sup>2+</sup> cations.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115093"},"PeriodicalIF":3.9,"publicationDate":"2025-04-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143776980","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}

引用次数: 0

Optimizing S-scheme heterojunctions of NiCo₂O₄ and graphdiyne-Cu₃P catalysts for enhanced photocatalytic hydrogen evolution

IF 3.9 2区化学 Q2 CHEMISTRY, PHYSICAL

Molecular Catalysis

Pub Date : 2025-04-04 DOI: 10.1016/j.mcat.2025.115087

Youlin Wu , Chaoyue Zheng , Qingyang Pang , Yanke Yang , Jia-Min Lu , Yiming Xie

The development of integrated photocatalysts to enhance the charge carrier separation efficiency of bimetallic oxides is a crucial strategy for achieving photocatalytic hydrogen production. In this study, the crystalline structure and synthesis results of NiCo₂O₄ and graphdiyne-Cu₃P (G-CP) catalysts were systematically investigated using X-ray diffraction and Raman spectroscopy. The Raman spectroscopic results confirmed the presence of graphite-like carbon nitride in G-CP, further validating the successful synthesis of the catalyst. Photoelectrochemical performance tests demonstrated that the heterojunction formed between G-CP and NiCo₂O₄ effectively reduced the recombination rates of charge carriers, with NCOGCP-80 exhibiting the highest photocurrent response intensity and the lowest resistance, indicating exceptional hydrogen evolution performance. In photocatalytic hydrogen evolution experiments, NCOGCP-80 achieved a hydrogen evolution amount of 312.22 µmol (6244.4 µmol·g⁻¹·h⁻¹), representing increases of 9.83 and 4.66 times compared to the individual catalysts. Finally, the formation of the S-scheme heterojunction between G-CP and NiCo₂O₄ is verified through theoretical calculations and in situ X-ray photoelectron spectroscopy.

{"title":"Optimizing S-scheme heterojunctions of NiCo₂O₄ and graphdiyne-Cu₃P catalysts for enhanced photocatalytic hydrogen evolution","authors":"Youlin Wu , Chaoyue Zheng , Qingyang Pang , Yanke Yang , Jia-Min Lu , Yiming Xie","doi":"10.1016/j.mcat.2025.115087","DOIUrl":"10.1016/j.mcat.2025.115087","url":null,"abstract":"<div><div>The development of integrated photocatalysts to enhance the charge carrier separation efficiency of bimetallic oxides is a crucial strategy for achieving photocatalytic hydrogen production. In this study, the crystalline structure and synthesis results of NiCo₂O₄ and graphdiyne-Cu₃P (G-CP) catalysts were systematically investigated using X-ray diffraction and Raman spectroscopy. The Raman spectroscopic results confirmed the presence of graphite-like carbon nitride in G-CP, further validating the successful synthesis of the catalyst. Photoelectrochemical performance tests demonstrated that the heterojunction formed between G-CP and NiCo₂O₄ effectively reduced the recombination rates of charge carriers, with NCOGCP-80 exhibiting the highest photocurrent response intensity and the lowest resistance, indicating exceptional hydrogen evolution performance. In photocatalytic hydrogen evolution experiments, NCOGCP-80 achieved a hydrogen evolution amount of 312.22 µmol (6244.4 µmol·g⁻¹·h⁻¹), representing increases of 9.83 and 4.66 times compared to the individual catalysts. Finally, the formation of the S-scheme heterojunction between G-CP and NiCo₂O₄ is verified through theoretical calculations and in situ X-ray photoelectron spectroscopy.</div></div>","PeriodicalId":393,"journal":{"name":"Molecular Catalysis","volume":"579 ","pages":"Article 115087"},"PeriodicalIF":3.9,"publicationDate":"2025-04-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143767596","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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