Pub Date : 2026-01-01DOI: 10.1016/S1872-2067(25)64869-8
Jinpeng Zhang , Teng Liang , Jaenudin Ridwan , Tian Chen , Elhussein M. Hashem , Meijun Guo , Amin Talebian-Kiakalaieh , Le Yu , Ping She , Jingrun Ran
Green hydrogen (H2) energy plays an important role in combating climate change, promoting energy transition, and fostering sustainable development. Solar-driven plastic photoreforming afford an attractive solution, it overcomes the limitation of the slow oxygen evolution half-reaction in overall water splitting while tackling environmental pollution and resource waste caused by plastics. However, this technology still rests on the experimental stage, and the transition from laboratory to realistic application remains lacking systematic view. In this review, key components for plastic photoreforming, including plastic pretreatment routes, photocatalysts exploration, basic photocatalytic modules for the realistic application, and feasibility, are investigated. Finally, outlook in this area is discussed.
{"title":"Key components for realistic application of plastic photoreforming coupled with H2 evolution","authors":"Jinpeng Zhang , Teng Liang , Jaenudin Ridwan , Tian Chen , Elhussein M. Hashem , Meijun Guo , Amin Talebian-Kiakalaieh , Le Yu , Ping She , Jingrun Ran","doi":"10.1016/S1872-2067(25)64869-8","DOIUrl":"10.1016/S1872-2067(25)64869-8","url":null,"abstract":"<div><div>Green hydrogen (H<sub>2</sub>) energy plays an important role in combating climate change, promoting energy transition, and fostering sustainable development. Solar-driven plastic photoreforming afford an attractive solution, it overcomes the limitation of the slow oxygen evolution half-reaction in overall water splitting while tackling environmental pollution and resource waste caused by plastics. However, this technology still rests on the experimental stage, and the transition from laboratory to realistic application remains lacking systematic view. In this review, key components for plastic photoreforming, including plastic pretreatment routes, photocatalysts exploration, basic photocatalytic modules for the realistic application, and feasibility, are investigated. Finally, outlook in this area is discussed.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 20-37"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915443","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}
Direct synthesis of dimethyl carbonate (DMC) from CO2 is critical for achieving carbon neutrality, yet the sluggish formation and conversion of the key *CH₃OCOO intermediate-due to the difficulty of C-O coupling-limit high DMC yields. Herein, we developed a boric acid-assisted recrystallization strategy to fabricate grain-boundary-rich CeO2 hollow nanospheres, which serve as an efficient catalyst for CO2 to DMC synthesis. The introduction of grain-boundary (GBs) induced the electron redistribution, which led a decrease in the electron density of bulk Ce ions and created a localized electron-rich region at homogeneous interface. This unique electronic landscape promoted reactive methoxy formation and stronger CO2 adsorption, thereby enabling more efficient coupling of *CH3O and *CO2 to form the *CH3OCOO. Concurrently, the enhanced CO2 adsorption facilitated the dissociation of *CH3OCOO and subsequent DMC formation. As a result, the 4%BCeO2-GBs achieved an advantageous DMC yield of 19.8 mmol/g. In the assistance of dehydrating agent, the catalyst delivered a remarkable 264.2 mmol/g DMC yield and 7.12% methanol conversion, which was 32 times higher than commercial CeO2. This study elucidated the intrinsic mechanisms governing *CH3OCOO intermediate behavior and offers valuable guidance for CO2 converting into high-value organic chemicals.
{"title":"Grain boundary engineering of CeO2 induced electron redistribution for dimethyl carbonate synthesis from CO2","authors":"Guoqiang Hou, Di Xu, Haifeng Fan, Yangyang Li, Siyi Huang, Mingyue Ding","doi":"10.1016/S1872-2067(25)64871-6","DOIUrl":"10.1016/S1872-2067(25)64871-6","url":null,"abstract":"<div><div>Direct synthesis of dimethyl carbonate (DMC) from CO<sub>2</sub> is critical for achieving carbon neutrality, yet the sluggish formation and conversion of the key *CH₃OCOO intermediate-due to the difficulty of C-O coupling-limit high DMC yields. Herein, we developed a boric acid-assisted recrystallization strategy to fabricate grain-boundary-rich CeO<sub>2</sub> hollow nanospheres, which serve as an efficient catalyst for CO<sub>2</sub> to DMC synthesis. The introduction of grain-boundary (GBs) induced the electron redistribution, which led a decrease in the electron density of bulk Ce ions and created a localized electron-rich region at homogeneous interface. This unique electronic landscape promoted reactive methoxy formation and stronger CO<sub>2</sub> adsorption, thereby enabling more efficient coupling of *CH<sub>3</sub>O and *CO<sub>2</sub> to form the *CH<sub>3</sub>OCOO. Concurrently, the enhanced CO<sub>2</sub> adsorption facilitated the dissociation of *CH<sub>3</sub>OCOO and subsequent DMC formation. As a result, the 4%BCeO<sub>2</sub>-GBs achieved an advantageous DMC yield of 19.8 mmol/g. In the assistance of dehydrating agent, the catalyst delivered a remarkable 264.2 mmol/g DMC yield and 7.12% methanol conversion, which was 32 times higher than commercial CeO<sub>2</sub>. This study elucidated the intrinsic mechanisms governing *CH<sub>3</sub>OCOO intermediate behavior and offers valuable guidance for CO<sub>2</sub> converting into high-value organic chemicals.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 316-329"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915446","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 : 2025-11-17DOI: 10.1016/S1872-2067(25)64846-7
Weijie Zhan, Nan Yang, Tong Zhou, Jin Zhang, Tianwei He, Qingju Liu
Solar-driven water splitting has emerged as a promising route for sustainable hydrogen generation, however, developing broad-spectrum responsive photocatalysts remains a challenge for achieving efficient solar-to-hydrogen conversion. Here, we demonstrate a g-C3N4 -based (UCN) catalyst with dispersed Ag single atoms (Ag SAs) and Ag nanoparticles (Ag NPs) for synergistically broad-spectrum photocatalytic hydrogen evolution. Experimental and theoretical results reveal that both Ag SAs and Ag NPs serve as active sites, with the Schottky junction between Ag NPs and g-C3N4 effectively promoting charge separation, while Ag NPs induce localized surface plasmon resonance, extending the light response range from visible to near-infrared regions. The optimized catalyst Ag-UCN-3 exhibits a hydrogen evolution rate as high as 22.11 mmol/g/h and an apparent quantum efficiency (AQE) of 10.16% under 420 nm light illumination. Notably, it still had a high hydrogen evolution rate of 633.57 μmol/g/h under 700 nm irradiation. This work unveils dual active sites engineering strategy that couples Ag SAs and Ag NPs with plasma and hot electrons, offering a new strategy for designing high-performance solar-driven energy systems.
{"title":"Construction of Ag single atoms and nanoparticles co-modified g-C3N4 for synergistic plasma photocatalytic broad-spectrum hydrogen production","authors":"Weijie Zhan, Nan Yang, Tong Zhou, Jin Zhang, Tianwei He, Qingju Liu","doi":"10.1016/S1872-2067(25)64846-7","DOIUrl":"10.1016/S1872-2067(25)64846-7","url":null,"abstract":"<div><div>Solar-driven water splitting has emerged as a promising route for sustainable hydrogen generation, however, developing broad-spectrum responsive photocatalysts remains a challenge for achieving efficient solar-to-hydrogen conversion. Here, we demonstrate a g-C<sub>3</sub>N<sub>4</sub> -based (UCN) catalyst with dispersed Ag single atoms (Ag SAs) and Ag nanoparticles (Ag NPs) for synergistically broad-spectrum photocatalytic hydrogen evolution. Experimental and theoretical results reveal that both Ag SAs and Ag NPs serve as active sites, with the Schottky junction between Ag NPs and g-C<sub>3</sub>N<sub>4</sub> effectively promoting charge separation, while Ag NPs induce localized surface plasmon resonance, extending the light response range from visible to near-infrared regions. The optimized catalyst Ag-UCN-3 exhibits a hydrogen evolution rate as high as 22.11 mmol/g/h and an apparent quantum efficiency (AQE) of 10.16% under 420 nm light illumination. Notably, it still had a high hydrogen evolution rate of 633.57 μmol/g/h under 700 nm irradiation. This work unveils dual active sites engineering strategy that couples Ag SAs and Ag NPs with plasma and hot electrons, offering a new strategy for designing high-performance solar-driven energy systems.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 162-173"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532475","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 : 2025-11-17DOI: 10.1016/S1872-2067(25)64843-1
Yuqing Yan , Yonghui Wu , Jun Wang , Jinrong Huo , Kai Yang , Kangqiang Lu
Constructing S-scheme heterojunctions preserves the intrinsic redox capabilities of both semiconductors while promoting the separation of photogenerated electrons and holes, making it a promising approach for enhancing the properties of semiconductors. In this study, an S-scheme Cd0.8Zn0.2S-CeO2 (CZS-CeO2) heterojunction was successfully fabricated via the in-situ growth of CZS nanowires on CeO2 nanocubes. The S-scheme charge-transfer mechanism of the CZS-CeO2 composites during photocatalytic reactions was confirmed through in-situ X-ray photoelectron spectroscopy and density functional theory calculations. These results demonstrate that the interfacial electric field (IEF) significantly facilitates charge separation and transport within the heterojunction. Consequently, the CZS-CeO2 composites exhibited excellent photocatalytic hydrogen production performance under simulated sunlight irradiation, surpassing that of blank CZS. Particularly, the optimal photocatalytic hydrogen generation rate for CZS-15%CeO2 reached 58 mmol·g–1·h–1, approximately 8.8 times higher than that of blank CZS. After five consecutive cycles of testing, CZS-15%CeO2 retained a relatively high level of activity. This enhanced stability can be attributed to the fabrication of S-scheme heterojunctions, which effectively suppressed hole-induced photocorrosion of CZS. This investigation provides a beneficial reference for the rational design of S-scheme heterojunction photocatalysts for efficient and stable photocatalytic hydrogen production.
{"title":"S-scheme Cd0.8Zn0.2S nanowires/CeO2 nanocubes heterojunction for efficient photocatalytic hydrogen evolution","authors":"Yuqing Yan , Yonghui Wu , Jun Wang , Jinrong Huo , Kai Yang , Kangqiang Lu","doi":"10.1016/S1872-2067(25)64843-1","DOIUrl":"10.1016/S1872-2067(25)64843-1","url":null,"abstract":"<div><div>Constructing S-scheme heterojunctions preserves the intrinsic redox capabilities of both semiconductors while promoting the separation of photogenerated electrons and holes, making it a promising approach for enhancing the properties of semiconductors. In this study, an S-scheme Cd<sub>0.8</sub>Zn<sub>0.2</sub>S-CeO<sub>2</sub> (CZS-CeO<sub>2</sub>) heterojunction was successfully fabricated via the <em>in-situ</em> growth of CZS nanowires on CeO<sub>2</sub> nanocubes. The S-scheme charge-transfer mechanism of the CZS-CeO<sub>2</sub> composites during photocatalytic reactions was confirmed through <em>in-situ</em> X-ray photoelectron spectroscopy and density functional theory calculations. These results demonstrate that the interfacial electric field (IEF) significantly facilitates charge separation and transport within the heterojunction. Consequently, the CZS-CeO<sub>2</sub> composites exhibited excellent photocatalytic hydrogen production performance under simulated sunlight irradiation, surpassing that of blank CZS. Particularly, the optimal photocatalytic hydrogen generation rate for CZS-15%CeO<sub>2</sub> reached 58 mmol·g<sup>–1</sup>·h<sup>–1</sup>, approximately 8.8 times higher than that of blank CZS. After five consecutive cycles of testing, CZS-15%CeO<sub>2</sub> retained a relatively high level of activity. This enhanced stability can be attributed to the fabrication of S-scheme heterojunctions, which effectively suppressed hole-induced photocorrosion of CZS. This investigation provides a beneficial reference for the rational design of S-scheme heterojunction photocatalysts for efficient and stable photocatalytic hydrogen production.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 231-239"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532534","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 : 2025-11-17DOI: 10.1016/S1872-2067(25)64835-2
Baofa Liu , Weijie Pan , Zhiyang Huang , Yi Zhao , Zuyang Luo , Tayirjan Taylor Isimjan , Bao Wang , Xiulin Yang
Designing exceptional-performance and long-lasting oxygen reduction reaction (ORR) catalysts is a critical challenge for the development of rechargeable Zn-air batteries (ZABs). In this study, we introduce a metal-free ORR catalyst composed of F–N co-doped hollow carbon (FNC), specifically engineered to address the limitations of conventional catalysts. The FNC catalysts were synthesized using a template-assisted pyrolysis method, resulting in a hollow, porous architecture with a high specific surface area and numerous active sites. Concurrently, F doping optimized the electronic configuration of pyridinic nitrogen. The introduction of C–F bonds reduced the reaction energy barrier, and the resulting N-C-F configuration enhanced the stability of the nitrogen center. The catalyst exhibits outstanding ORR activity in alkaline media, exhibiting a half-wave potential (E1/2) of 0.87 V, surpassing that of commercial Pt/C (E1/2 = 0.85 V). When applied to both aqueous and flexible ZAB configurations, the FNC catalyst achieved peak power densities of 172 and 85 mW cm–2, respectively, along with exceptional cycling stabilities exceeding 5300 and 302 h, respectively. This study establishes a novel approach for designing metal-free ORR catalysts and next-generation ZABs, particularly for use in flexible and wearable microelectronic devices.
{"title":"Unlocking 5300-h ultrastable metal-free ORR catalysts for Zn-air batteries via F–N co-doped tailored carbon pore architectures and synergistic adsorption modulation","authors":"Baofa Liu , Weijie Pan , Zhiyang Huang , Yi Zhao , Zuyang Luo , Tayirjan Taylor Isimjan , Bao Wang , Xiulin Yang","doi":"10.1016/S1872-2067(25)64835-2","DOIUrl":"10.1016/S1872-2067(25)64835-2","url":null,"abstract":"<div><div>Designing exceptional-performance and long-lasting oxygen reduction reaction (ORR) catalysts is a critical challenge for the development of rechargeable Zn-air batteries (ZABs). In this study, we introduce a metal-free ORR catalyst composed of F–N co-doped hollow carbon (FNC), specifically engineered to address the limitations of conventional catalysts. The FNC catalysts were synthesized using a template-assisted pyrolysis method, resulting in a hollow, porous architecture with a high specific surface area and numerous active sites. Concurrently, F doping optimized the electronic configuration of pyridinic nitrogen. The introduction of C–F bonds reduced the reaction energy barrier, and the resulting N-C-F configuration enhanced the stability of the nitrogen center. The catalyst exhibits outstanding ORR activity in alkaline media, exhibiting a half-wave potential (<em>E</em><sub>1/2</sub>) of 0.87 V, surpassing that of commercial Pt/C (<em>E</em><sub>1/2</sub> = 0.85 V). When applied to both aqueous and flexible ZAB configurations, the FNC catalyst achieved peak power densities of 172 and 85 mW cm<sup>–2</sup>, respectively, along with exceptional cycling stabilities exceeding 5300 and 302 h, respectively. This study establishes a novel approach for designing metal-free ORR catalysts and next-generation ZABs, particularly for use in flexible and wearable microelectronic devices.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 100-111"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532597","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 : 2025-11-17DOI: 10.1016/S1872-2067(25)64820-0
Jiachen Wu, Pengfei Liu, Huagui Yang
Membrane electrode assemblies (MEAs) represent the preeminent configuration for industrial-scale CO2 electrolysis, yet their dynamic interfaces and degradation pathways remain inadequately resolved. This perspective highlights how advanced operando characterization techniques—synchrotron X-ray spectroscopy, spatially resolved X-ray fluorescence, vibrational spectroscopy, electrochemical diagnostics et al.—decipher atomic-scale catalyst evolution, transient ion/water fluxes, and extreme interfacial microenvironments under industrial current densities. These methodologies reveal critical degradation mechanisms, including catalyst restructuring, carbonate precipitation-driven flooding, and cation-induced pH gradients, which are inaccessible to conventional ex-situ or three-electrode analyses. Integrating multimodal characterization is paramount to correlate transient interfacial chemistry with system-level performance, guiding the rational design of durable, high-selectivity MEAs for scalable CO2 conversion.
{"title":"In-situ and operando characterizations in membrane electrode assemblies: Resolving dynamic interfaces and degradation pathways in CO2 electrocatalysis","authors":"Jiachen Wu, Pengfei Liu, Huagui Yang","doi":"10.1016/S1872-2067(25)64820-0","DOIUrl":"10.1016/S1872-2067(25)64820-0","url":null,"abstract":"<div><div>Membrane electrode assemblies (MEAs) represent the preeminent configuration for industrial-scale CO<sub>2</sub> electrolysis, yet their dynamic interfaces and degradation pathways remain inadequately resolved. This perspective highlights how advanced <em>operando</em> characterization techniques—synchrotron X-ray spectroscopy, spatially resolved X-ray fluorescence, vibrational spectroscopy, electrochemical diagnostics <em>et al</em>.—decipher atomic-scale catalyst evolution, transient ion/water fluxes, and extreme interfacial microenvironments under industrial current densities. These methodologies reveal critical degradation mechanisms, including catalyst restructuring, carbonate precipitation-driven flooding, and cation-induced pH gradients, which are inaccessible to conventional <em>ex-situ</em> or three-electrode analyses. Integrating multimodal characterization is paramount to correlate transient interfacial chemistry with system-level performance, guiding the rational design of durable, high-selectivity MEAs for scalable CO<sub>2</sub> conversion.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 1-8"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532535","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 : 2025-11-17DOI: 10.1016/S1872-2067(25)64852-2
Hao Wu , Xian Jiang , Jingyu Lu , Yibo Li , Xinyan Li , Guidong Ju , Rengui Li , Jing Zhang
The hydrogen evolution reaction (HER) in alkaline water electrolysis faces significant kinetic and thermodynamic challenges that hinder its efficiency and scalability for sustainable hydrogen production. Herein, we employed an in-situ synthesis strategy to incorporate H atoms into the PdRu alloy lattice to form HInc-PdRu electrocatalyst, thereby modulating its electronic structure and enhancing its alkaline HER performance. We demonstrate that the incorporation of H atoms significantly improves electrocatalytic activity, achieving a remarkably low overpotential of 25 mV at 10 mA cm–2 compared with the Pd, Ru and PdRu catalysts while maintaining robust catalyst stability. Operando spectroscopic analysis indicates that H insertion into the HInc-PdRu electrocatalyst enhances the availability of H2O* at the surface, promoting water dissociation at the active sites. Theoretical calculations proposed that the co-incorporating H and Ru atoms induces s-d orbital coupling within the Pd lattices, effectively weakening hydrogen adsorption strength and optimizing the alkaline HER energetics. This work presents a facile approach for the rational design of bimetallic electrocatalysts for efficient and stable alkaline water electrolysis for renewable hydrogen production.
碱水电解中的析氢反应（HER）面临着显著的动力学和热力学挑战，阻碍了其效率和可扩展性，以实现可持续的制氢。本文采用原位合成策略，将H原子加入到PdRu合金晶格中，形成hhc -PdRu电催化剂，从而调节其电子结构，提高其碱性HER性能。我们证明了H原子的加入显著提高了电催化活性，与Pd、Ru和PdRu催化剂相比，在10 mA cm-2下实现了25 mV的过电位，同时保持了强大的催化剂稳定性。Operando光谱分析表明，H插入到hinch - pdru电催化剂中，提高了表面H2O*的可用性，促进了活性位点的水解离。理论计算表明，H和Ru原子的共结合在Pd晶格内诱导了s-d轨道耦合，有效地削弱了氢的吸附强度，优化了碱性HER的能量学。本研究为合理设计双金属电催化剂提供了一种简便的方法，可用于高效、稳定的碱性电解再生制氢。
{"title":"H-incorporated PdRu electrocatalyst for water splitting under alkaline condition","authors":"Hao Wu , Xian Jiang , Jingyu Lu , Yibo Li , Xinyan Li , Guidong Ju , Rengui Li , Jing Zhang","doi":"10.1016/S1872-2067(25)64852-2","DOIUrl":"10.1016/S1872-2067(25)64852-2","url":null,"abstract":"<div><div>The hydrogen evolution reaction (HER) in alkaline water electrolysis faces significant kinetic and thermodynamic challenges that hinder its efficiency and scalability for sustainable hydrogen production. Herein, we employed an <em>in-situ</em> synthesis strategy to incorporate H atoms into the PdRu alloy lattice to form H<sub>Inc</sub>-PdRu electrocatalyst, thereby modulating its electronic structure and enhancing its alkaline HER performance. We demonstrate that the incorporation of H atoms significantly improves electrocatalytic activity, achieving a remarkably low overpotential of 25 mV at 10 mA cm<sup>–2</sup> compared with the Pd, Ru and PdRu catalysts while maintaining robust catalyst stability. Operando spectroscopic analysis indicates that H insertion into the H<sub>Inc</sub>-PdRu electrocatalyst enhances the availability of H<sub>2</sub>O* at the surface, promoting water dissociation at the active sites. Theoretical calculations proposed that the co-incorporating H and Ru atoms induces s-d orbital coupling within the Pd lattices, effectively weakening hydrogen adsorption strength and optimizing the alkaline HER energetics. This work presents a facile approach for the rational design of bimetallic electrocatalysts for efficient and stable alkaline water electrolysis for renewable hydrogen production.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 91-99"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532596","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 : 2025-11-17DOI: 10.1016/S1872-2067(25)64847-9
Junru Xu , Lei Cheng , Tongming Su , Yawen Tang , Hanjun Sun
All-organic intermolecular S-scheme heterojunction photocatalysts are promising for efficient and fast carrier separation, yet attaining strong reducing capacity and tracking directional charge transfer remain critical challenges. Herein, we unveiled an intermolecular S-scheme heterojunction through in-situ growth of conjugated poly(1,4-diethynylbenzene) (pDEB, reduction photocatalyst) on graphitic carbon nitride (g-C3N4, oxidation photocatalyst), forming the nanofiber-decorated nanosheet-like pDEB/CN architecture via π-conjugated polymer templating. By leveraging the electron-donating effect and the expanded π-electron delocalization range of electron-rich conjugated acetylenic polymers, pDEB with high energy band positions was introduced into the intermolecular S-scheme heterojunction with enhanced reducibility. The directional S-scheme charge migration is mechanistically demonstrated by deploying dual metal oxide cocatalysts as spatially resolved electron donor-acceptor probes, with light-modulated in-situ X-ray photoelectron spectroscopy capturing real-time interfacial charge migration. Femtosecond transient absorption spectroscopy further elucidates accelerated ultrafast electron transfer kinetics mediated by the S-scheme interfacial electric field. The S-scheme heterojunction attained an apparent quantum efficiency of 5.18% at 420 nm during the photocatalytic H2O2 production. Notably, pDEB/CN has demonstrated an excellent H2O2 yield for the first time in a continuous flow photocatalytic system, reaching 394.27 μmol g–1 h–1 within 24 h, which illustrates the stable interfacial charge transfer brought about by the rigid structure. The work demonstrated the transformative potential of architecting directional charge superhighways through band level engineering, while advancing S-scheme heterojunctions design with molecular precision.
全有机分子间s型异质结光催化剂有望实现高效、快速的载流子分离，但获得强大的还原能力和跟踪定向电荷转移仍然是关键的挑战。在此，我们通过原位生长共轭聚（1,4-二乙基苯）（pDEB，还原光催化剂）在石墨氮化碳（g-C3N4，氧化光催化剂）上形成分子间S-scheme异质结，通过π共轭聚合物模板形成纳米纤维装饰的纳米片状pDEB/CN结构。利用富电子共轭乙炔聚合物的给电子效应和扩大π-电子离域范围，将具有高能带位的pDEB引入分子间s型异质结中，增强了还原性。通过将双金属氧化物共催化剂作为空间分辨的电子供体-受体探针，利用光调制的原位x射线光电子能谱捕捉实时界面电荷迁移，可以从机理上证明定向s方案的电荷迁移。飞秒瞬态吸收光谱进一步阐明了s型界面电场介导的加速超快电子转移动力学。在光催化制H2O2过程中，s型异质结在420 nm处的表观量子效率为5.18%。值得注意的是，pDEB/CN在连续流光催化体系中首次表现出优异的H2O2产率，在24 h内达到394.27 μmol g-1 h - 1，说明刚性结构带来了稳定的界面电荷转移。这项工作展示了通过波段级工程构建定向电荷高速公路的变革潜力，同时推进了具有分子精度的s方案异质结设计。
{"title":"Band-gap engineered intermolecular S-scheme heterojunctions: π-conjugated acetylenic polymers/g-C3N4 with ultrafast charge transfer for solar-driven H2O2 synthesis","authors":"Junru Xu , Lei Cheng , Tongming Su , Yawen Tang , Hanjun Sun","doi":"10.1016/S1872-2067(25)64847-9","DOIUrl":"10.1016/S1872-2067(25)64847-9","url":null,"abstract":"<div><div>All-organic intermolecular S-scheme heterojunction photocatalysts are promising for efficient and fast carrier separation, yet attaining strong reducing capacity and tracking directional charge transfer remain critical challenges. Herein, we unveiled an intermolecular S-scheme heterojunction through <em>in-situ</em> growth of conjugated poly(1,4-diethynylbenzene) (pDEB, reduction photocatalyst) on graphitic carbon nitride (<em>g</em>-C<sub>3</sub>N<sub>4</sub>, oxidation photocatalyst), forming the nanofiber-decorated nanosheet-like pDEB/CN architecture <em>via</em> π-conjugated polymer templating. By leveraging the electron-donating effect and the expanded π-electron delocalization range of electron-rich conjugated acetylenic polymers, pDEB with high energy band positions was introduced into the intermolecular S-scheme heterojunction with enhanced reducibility. The directional S-scheme charge migration is mechanistically demonstrated by deploying dual metal oxide cocatalysts as spatially resolved electron donor-acceptor probes, with light-modulated <em>in-situ</em> X-ray photoelectron spectroscopy capturing real-time interfacial charge migration. Femtosecond transient absorption spectroscopy further elucidates accelerated ultrafast electron transfer kinetics mediated by the S-scheme interfacial electric field. The S-scheme heterojunction attained an apparent quantum efficiency of 5.18% at 420 nm during the photocatalytic H<sub>2</sub>O<sub>2</sub> production. Notably, pDEB/CN has demonstrated an excellent H<sub>2</sub>O<sub>2</sub> yield for the first time in a continuous flow photocatalytic system, reaching 394.27 μmol g<sup>–1</sup> h<sup>–1</sup> within 24 h, which illustrates the stable interfacial charge transfer brought about by the rigid structure. The work demonstrated the transformative potential of architecting directional charge superhighways through band level engineering, while advancing S-scheme heterojunctions design with molecular precision.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 205-218"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532532","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 : 2025-11-17DOI: 10.1016/S1872-2067(25)64848-0
Xi Chen , Wei Jin , Xinyu Zhong , Hongqiao Lin , Junjie Ding , Xinyu Liu , Hui Wang , Fasheng Chen , Yan Xiong , Changchun Ding , Zhong Jin , Minghang Jiang
In this paper we report the preparation of nano-dendritic Cu₂O/Cu heterojunctions doped with varying concentrations of cobalt through a convenient, energy-consumption-free, and environmentally friendly chemical replacement method. The analysis results reveal that the incorporation of cobalt in its atomic form enhances the adsorption of nitrate species onto the catalyst surface, whereas doping with metallic cobalt promotes the production of active hydrogen (*H). By adjusting the doping concentration of cobalt, we effectively control its doping form (atomic and metallic states) on the surface of dendritic copper, thereby enabling controllable modulation of the active hydrogen concentration on the catalyst surface. By ensuring sufficient consumption of *H during the NITRR process while avoiding excessively high concentrations that could trigger detrimental hydrogen evolution reaction side reactions, this approach remarkably enhances the selectivity of ammonia synthesis in NITRR. This study offers an effective approach to regulate the *H concentration on the surface of the catalyst through adjusting the metal doping form, thereby improving the performance of ammonia synthesis from NITRR.
{"title":"Optimized kinetic pathways of active hydrogen generation at Cu2O/Cu heterojunction interfaces to enhance nitrate electroreduction to ammonia","authors":"Xi Chen , Wei Jin , Xinyu Zhong , Hongqiao Lin , Junjie Ding , Xinyu Liu , Hui Wang , Fasheng Chen , Yan Xiong , Changchun Ding , Zhong Jin , Minghang Jiang","doi":"10.1016/S1872-2067(25)64848-0","DOIUrl":"10.1016/S1872-2067(25)64848-0","url":null,"abstract":"<div><div>In this paper we report the preparation of nano-dendritic Cu₂O/Cu heterojunctions doped with varying concentrations of cobalt through a convenient, energy-consumption-free, and environmentally friendly chemical replacement method. The analysis results reveal that the incorporation of cobalt in its atomic form enhances the adsorption of nitrate species onto the catalyst surface, whereas doping with metallic cobalt promotes the production of active hydrogen (*H). By adjusting the doping concentration of cobalt, we effectively control its doping form (atomic and metallic states) on the surface of dendritic copper, thereby enabling controllable modulation of the active hydrogen concentration on the catalyst surface. By ensuring sufficient consumption of *H during the NITRR process while avoiding excessively high concentrations that could trigger detrimental hydrogen evolution reaction side reactions, this approach remarkably enhances the selectivity of ammonia synthesis in NITRR. This study offers an effective approach to regulate the *H concentration on the surface of the catalyst through adjusting the metal doping form, thereby improving the performance of ammonia synthesis from NITRR.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 78-90"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532595","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 : 2025-11-17DOI: 10.1016/S1872-2067(25)64849-2
Lihong Tan , Xinhe Wu , Jiachao Xu , Mahmoud Sayed , Guohong Wang
The construction of crystalline/amorphous g-C3N4 homojunctions presents a versatile strategy to obtain all-organic homojunction photocatalysts with better interface matching and lower interface charge carrier movement resistance for optimized photocatalytic activity. However, the process entails a complex multi-step workup, which compromises its feasibility. To overcome this challenge, this work provided an innovative Na2CO3-induced crystallinity modulation strategy to construct a Na-doped crystalline/amorphous g-C3N4 S-scheme homojunction photocatalyst in a single step. The approach involves the initial pre-assembling of melamine and cyanuric acid molecules, and subsequent introduction of Na2CO3 before the calcination. Na2CO3 plays key roles to induce in-situ crystallinity modulation during the calcination and as a source for Na-doping. The prepared g-C3N4 S-scheme homojunction photocatalyst demonstrated a prominent H2O2-production rate of 444.6 μmol·L–1·h–1, which is 6.1-fold higher than that of bulk g-C3N4. The enhanced activity was attributed to the synergistic effect of charge carrier separation induced by the S-scheme homojunction system, and the optimized interfacial H2O2 generation kinetics. The latter was fostered by the Na-doping. This study provides an innovative approach for the one-step construction of g-C3N4 S-scheme homojunction and its integration in photocatalytic applications.
构建晶态/非晶态g-C3N4同质结是获得具有较好界面匹配和较低界面载流子移动阻力的全有机同质结光催化剂的一种通用策略，可优化光催化活性。然而，这个过程需要一个复杂的多步骤的工作，这损害了其可行性。为了克服这一挑战，本工作提供了一种创新的na2co3诱导结晶度调制策略，以一步构建na掺杂晶体/非晶g- c3n4s -scheme同质结光催化剂。该方法包括最初的三聚氰胺和三聚氰尿酸分子的预组装，随后在煅烧前引入Na2CO3。在煅烧过程中，Na2CO3在诱导原位结晶度调制中起着关键作用，并作为na掺杂的来源。制备的g-C3N4 s -方案均结光催化剂的h2o2产率为444.6 μmol·L-1·h-1，是本体g-C3N4的6.1倍。活性的增强主要是由于s -图式均结体系诱导的载流子分离的协同作用，以及优化的界面H2O2生成动力学。后者是由钠兴奋剂促成的。本研究为一步构建g-C3N4 s -图式均结及其在光催化应用中的集成提供了一种创新方法。
{"title":"Na2CO3-assisted synthesis of Na-doped crystalline/amorphous g-C3N4 S-scheme homojunction photocatalyst for enhanced H2O2 production","authors":"Lihong Tan , Xinhe Wu , Jiachao Xu , Mahmoud Sayed , Guohong Wang","doi":"10.1016/S1872-2067(25)64849-2","DOIUrl":"10.1016/S1872-2067(25)64849-2","url":null,"abstract":"<div><div>The construction of crystalline/amorphous g-C<sub>3</sub>N<sub>4</sub> homojunctions presents a versatile strategy to obtain all-organic homojunction photocatalysts with better interface matching and lower interface charge carrier movement resistance for optimized photocatalytic activity. However, the process entails a complex multi-step workup, which compromises its feasibility. To overcome this challenge, this work provided an innovative Na<sub>2</sub>CO<sub>3</sub>-induced crystallinity modulation strategy to construct a Na-doped crystalline/amorphous g-C<sub>3</sub>N<sub>4</sub> S-scheme homojunction photocatalyst in a single step. The approach involves the initial pre-assembling of melamine and cyanuric acid molecules, and subsequent introduction of Na<sub>2</sub>CO<sub>3</sub> before the calcination. Na<sub>2</sub>CO<sub>3</sub> plays key roles to induce <em>in-situ</em> crystallinity modulation during the calcination and as a source for Na-doping. The prepared g-C<sub>3</sub>N<sub>4</sub> S-scheme homojunction photocatalyst demonstrated a prominent H<sub>2</sub>O<sub>2</sub>-production rate of 444.6 μmol·L<sup>–1</sup>·h<sup>–1</sup>, which is 6.1-fold higher than that of bulk g-C<sub>3</sub>N<sub>4</sub>. The enhanced activity was attributed to the synergistic effect of charge carrier separation induced by the S-scheme homojunction system, and the optimized interfacial H<sub>2</sub>O<sub>2</sub> generation kinetics. The latter was fostered by the Na-doping. This study provides an innovative approach for the one-step construction of g-C<sub>3</sub>N<sub>4</sub> S-scheme homojunction and its integration in photocatalytic applications.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 174-185"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532476","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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