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}
Pub Date : 2025-11-17DOI: 10.1016/S1872-2067(25)64759-0
Yuxing Xu , Leilei Wang , Qin Liu , Botao Teng , Chuanqiang Wu , Binghui Ge , Wentuan Bi , Minghui Gu , Mengkai Zhang , Huan Yan , Junling Lu
Electrocatalytic conversion of carbon dioxide (CO2) offers an effective method of CO2 fixation to mitigate global warming and the energy crisis. However, for supported Ni single-atom catalysts (SACs), which are among the most promising candidates for this application, the relationship between Ni coordination structure and catalytic properties is still under strong debate. Here, we fabricated a series of Ni SACs through precise-engineering of anchor sites on nitrogen-doped carbon (NC) followed by Ni atom anchoring using atomic layer deposition. Among them, a Ni1/NC SAC, with a coordination number (CN) of four but less pyridinic nitrogen (Npyri), achieved over 90% faradaic efficiency for CO at potentials from –0.7 to –1.0 V and a mass activity of 6.5 A/mgNi at –0.78 V along with high stability, outperforming other Ni SACs with lower CN and more Npyri. Theoretical calculations of various three and four-coordinated Ni1-NxCy structures revealed a linear correlation between the reaction Gibbs free energy for the potential–limiting step and the highest occupied molecular orbital (HOMO) position of Ni-3d orbitals, therein the four-coordinated Ni1-N1C3 with the highest HOMO position is identified as the active site for the electrocatalytic CO2-to-CO process, in line with the experimental results.
二氧化碳的电催化转化为减缓全球变暖和能源危机提供了一种有效的二氧化碳固定方法。然而，对于负载型镍单原子催化剂（SACs）来说，镍配位结构与催化性能之间的关系仍然存在激烈的争论。在这里，我们通过在氮掺杂碳（NC）上精确设计锚点，然后使用原子层沉积技术将Ni原子锚定，从而制备了一系列Ni SACs。其中，配位数（CN）为4而吡啶氮（Npyri）较少的Ni1/NC SAC在-0.7 ~ -1.0 V电势下对CO的法拉第效率超过90%，在-0.78 V电势下的质量活度为6.5 a /mgNi，稳定性好，优于其他CN较低、Npyri较高的Ni SAC。对各种三配位和四配位Ni1-NxCy结构的理论计算表明，限制电位步骤反应的吉布斯自由能与Ni-3d轨道的最高占据分子轨道（HOMO）位置呈线性相关，其中HOMO位置最高的四配位Ni1-N1C3被确定为电催化CO2-to-CO过程的活性位点，与实验结果一致。
{"title":"Integrating controlled synthesis and theory for revealing of active site structure of single-atom nickel catalysts in electrochemical CO2 reduction","authors":"Yuxing Xu , Leilei Wang , Qin Liu , Botao Teng , Chuanqiang Wu , Binghui Ge , Wentuan Bi , Minghui Gu , Mengkai Zhang , Huan Yan , Junling Lu","doi":"10.1016/S1872-2067(25)64759-0","DOIUrl":"10.1016/S1872-2067(25)64759-0","url":null,"abstract":"<div><div>Electrocatalytic conversion of carbon dioxide (CO<sub>2</sub>) offers an effective method of CO<sub>2</sub> fixation to mitigate global warming and the energy crisis. However, for supported Ni single-atom catalysts (SACs), which are among the most promising candidates for this application, the relationship between Ni coordination structure and catalytic properties is still under strong debate. Here, we fabricated a series of Ni SACs through precise-engineering of anchor sites on nitrogen-doped carbon (NC) followed by Ni atom anchoring using atomic layer deposition. Among them, a Ni<sub>1</sub>/NC SAC, with a coordination number (CN) of four but less pyridinic nitrogen (N<sub>pyri</sub>), achieved over 90% faradaic efficiency for CO at potentials from –0.7 to –1.0 V and a mass activity of 6.5 A/mg<sub>Ni</sub> at –0.78 V along with high stability, outperforming other Ni SACs with lower CN and more N<sub>pyri</sub>. Theoretical calculations of various three and four-coordinated Ni<sub>1</sub>-N<sub><em>x</em></sub>C<sub><em>y</em></sub> structures revealed a linear correlation between the reaction Gibbs free energy for the potential–limiting step and the highest occupied molecular orbital (HOMO) position of Ni-3<em>d</em> orbitals, therein the four-coordinated Ni<sub>1</sub>-N<sub>1</sub>C<sub>3</sub> with the highest HOMO position is identified as the active site for the electrocatalytic CO<sub>2</sub>-to-CO process, in line with the experimental results.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 68-77"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532594","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)64844-3
Yinhong Niu , Zhen Shi , Zhiquan Yu , Qiang Guo , Junju Mu , Yafei Liang , Zhixin Zhang , Sheng Wang , Feng Wang
Vanadium phosphorus oxide (VPO) catalyst is a promising candidate for the condensation reaction of formaldehyde (FA) and acetic acid (HAc) to produce acrylic acid (AA). However, the complexity of the active phases and their dynamic interconversion under redox conditions has led to controversies regarding the actual active phase in this reaction. To address this, this study systematically investigates the phase transition and underlying mechanism of VPO catalysts under reaction conditions. X-ray diffraction (XRD) patterns, Raman spectra, transmission electron microscopy images and X-ray photoelectron spectroscopy collectively demonstrated that the V4+ phase (VO)2P2O7 retained the bulk phase structure throughout the reaction, with only minor surface phase transition observed. In contrast, the V5+ phase underwent reduction to other phases in both bulk and surface regions. Specifically, the δ-VOPO4 phase rapidly transformed into the αII-VOPO4 phase, which could reversibly convert into the R1-VOHPO4 phase (V4+). Controlled variable experiments, H2-temperature programmed reduction and in-situ XRD experiments in a hydrogen atmosphere further demonstrated that these phase transitions were primarily attributed to the loss of lattice oxygen. The presence of V4+ phase in VPO catalysts enhanced the selectivity of acrylic acid, while the existence of V5+ phase promoted the activation of acetic acid. This work elucidates the redox-driven phase evolution of VPO catalysts and offers valuable insights for designing efficient catalysts for FA-HAc cross-condensation by balancing phase stability and activity.
{"title":"Lattice oxygen transfer induced active phase transition of VPO catalysts in cross condensation of acetic acid and formaldehyde","authors":"Yinhong Niu , Zhen Shi , Zhiquan Yu , Qiang Guo , Junju Mu , Yafei Liang , Zhixin Zhang , Sheng Wang , Feng Wang","doi":"10.1016/S1872-2067(25)64844-3","DOIUrl":"10.1016/S1872-2067(25)64844-3","url":null,"abstract":"<div><div>Vanadium phosphorus oxide (VPO) catalyst is a promising candidate for the condensation reaction of formaldehyde (FA) and acetic acid (HAc) to produce acrylic acid (AA). However, the complexity of the active phases and their dynamic interconversion under redox conditions has led to controversies regarding the actual active phase in this reaction. To address this, this study systematically investigates the phase transition and underlying mechanism of VPO catalysts under reaction conditions. X-ray diffraction (XRD) patterns, Raman spectra, transmission electron microscopy images and X-ray photoelectron spectroscopy collectively demonstrated that the V<sup>4+</sup> phase (VO)<sub>2</sub>P<sub>2</sub>O<sub>7</sub> retained the bulk phase structure throughout the reaction, with only minor surface phase transition observed. In contrast, the V<sup>5+</sup> phase underwent reduction to other phases in both bulk and surface regions. Specifically, the <em>δ</em>-VOPO<sub>4</sub> phase rapidly transformed into the <em>α</em><sub>II</sub>-VOPO<sub>4</sub> phase, which could reversibly convert into the R1-VOHPO<sub>4</sub> phase (V<sup>4+</sup>). Controlled variable experiments, H<sub>2</sub>-temperature programmed reduction and <em>in-situ</em> XRD experiments in a hydrogen atmosphere further demonstrated that these phase transitions were primarily attributed to the loss of lattice oxygen. The presence of V<sup>4+</sup> phase in VPO catalysts enhanced the selectivity of acrylic acid, while the existence of V<sup>5+</sup> phase promoted the activation of acetic acid. This work elucidates the redox-driven phase evolution of VPO catalysts and offers valuable insights for designing efficient catalysts for FA-HAc cross-condensation by balancing phase stability and activity.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 112-126"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532506","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)64817-0
Haotian Guo , Lulu Zhao , Xinyu Liu , Jing Li , Pengfei Wang , Zonglin Liu , Linlin Wang , Jie Shu , Tingfeng Yi
Metal-organic frameworks (MOFs) are porous materials formed by the coordination of organic and inorganic components through coordination bonds. MOF-derived materials preserve the large surface area and inherent porosity of their parent structures, while simultaneously offering enhanced electrical conductivity and more efficient charge transport. Studies have shown that integrating electrospinning with MOFs into continuous nanofiber networks can effectively address issues such as MOF structural collapse, low conductivity, and leaching of active sites. Moreover, the electrospinning technique enables fine-tuning of the product’s morphology, architecture, and chemical composition, thereby unlocking new possibilities for advancing high-performance ZABs. This review provides a systematic overview of recent advances in non-precious metal electrocatalysts derived from electrospun-MOF composites and examines the unique advantages of combining electrospinning with MOF precursors in the design of oxygen electrocatalysts. It also investigates the morphological regulation of various fiber structures, including porous, hollow, core-shell, and beaded structures, as well as their influence on the catalytic performance. Finally, the performance enhancement strategies of electrospun-MOF catalyst materials are examined, and the development prospects along with future research directions related to oxygen electrocatalysts based on electrospun nanofibers are emphasized. This thorough review aims to offer meaningful insights and practical guidance for advancing the understanding, design, and fabrication of next-generation devices for energy conversion and storage.
{"title":"Electrospinning technology combined with MOFs: Bridging the development of high-performance zinc-air batteries","authors":"Haotian Guo , Lulu Zhao , Xinyu Liu , Jing Li , Pengfei Wang , Zonglin Liu , Linlin Wang , Jie Shu , Tingfeng Yi","doi":"10.1016/S1872-2067(25)64817-0","DOIUrl":"10.1016/S1872-2067(25)64817-0","url":null,"abstract":"<div><div>Metal-organic frameworks (MOFs) are porous materials formed by the coordination of organic and inorganic components through coordination bonds. MOF-derived materials preserve the large surface area and inherent porosity of their parent structures, while simultaneously offering enhanced electrical conductivity and more efficient charge transport. Studies have shown that integrating electrospinning with MOFs into continuous nanofiber networks can effectively address issues such as MOF structural collapse, low conductivity, and leaching of active sites. Moreover, the electrospinning technique enables fine-tuning of the product’s morphology, architecture, and chemical composition, thereby unlocking new possibilities for advancing high-performance ZABs. This review provides a systematic overview of recent advances in non-precious metal electrocatalysts derived from electrospun-MOF composites and examines the unique advantages of combining electrospinning with MOF precursors in the design of oxygen electrocatalysts. It also investigates the morphological regulation of various fiber structures, including porous, hollow, core-shell, and beaded structures, as well as their influence on the catalytic performance. Finally, the performance enhancement strategies of electrospun-MOF catalyst materials are examined, and the development prospects along with future research directions related to oxygen electrocatalysts based on electrospun nanofibers are emphasized. This thorough review aims to offer meaningful insights and practical guidance for advancing the understanding, design, and fabrication of next-generation devices for energy conversion and storage.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 32-67"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532593","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)64841-8
Yan Wang , Xiaorui Yan , Zeyang Sun , Jinjun Liu , Yiwen Wang , Chenchao Hu , Yilin Deng , Meng Xie , Jimin Xie , Wei Zhang , Yuanguo Xu
The regulation of peroxymonosulfate (PMS) activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle. This work demonstrates a strategy to constructed ethylene glycol (EG) well-coupled S-scheme heterojunction of NiFe2O4–x/NiS with oxygen vacancy (VO)-modified to efficiently achieve pollutant removal by activating PMS through photoexcitation, a 99% PMS decomposition efficiency is achieved. Photoassisted Kelvin probe force microscopy and in-situ electron spin resonance verify the establishment of a charge-transfer pathway consistent in NiFe2O4–x/NiS with an S-scheme heterojunction, which dramatically provides abundant active sites and distinct charge transport pathway for organic pollutant oxidation. The S-scheme NiFe2O4–x/NiS heterojunction in the photo-Fenton-like system exhibited significantly enhanced degradation rate (0.15 min–1) at a low PMS dosage of 0.1 g/L, which is 19 times greater than that of the pristine NiS (0.0077 min–1). Density functional theory calculations confirmed that VO in NiFe2O4–x/NiS efficiently promoted PMS adsorption and lowered the energy barrier for electron transfer. Moreover, in-situ experiments and experimental evidence offer mechanistic insights into the PMS activation through photoexcitation, unraveling a dual-pathway activation mechanism involving reduction and oxidation processes over NiFe2O4–x/NiS during the reaction. This work emphasizes the potential of vacancy engineering synergistic S-scheme heterojunction in developing efficient catalysts for regulating PMS activation, providing a promising solution the cost-effective and efficient treatment of organic wastewater.
{"title":"Synergistic catalysis of oxygen vacancy and S-scheme heterojunction in NiFe2O4–x/NiS regulates peroxymonosulfate activation forenhanced photo-Fenton-like reaction","authors":"Yan Wang , Xiaorui Yan , Zeyang Sun , Jinjun Liu , Yiwen Wang , Chenchao Hu , Yilin Deng , Meng Xie , Jimin Xie , Wei Zhang , Yuanguo Xu","doi":"10.1016/S1872-2067(25)64841-8","DOIUrl":"10.1016/S1872-2067(25)64841-8","url":null,"abstract":"<div><div>The regulation of peroxymonosulfate (PMS) activation by constructing oxygen vacancy and heterogeneous interface catalytic is crucial towards the oxidation of refractory pollutants still remains a major hurdle. This work demonstrates a strategy to constructed ethylene glycol (EG) well-coupled S-scheme heterojunction of NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS with oxygen vacancy (V<sub>O</sub>)-modified to efficiently achieve pollutant removal by activating PMS through photoexcitation, a 99% PMS decomposition efficiency is achieved. Photoassisted Kelvin probe force microscopy and <em>in-situ</em> electron spin resonance verify the establishment of a charge-transfer pathway consistent in NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS with an S-scheme heterojunction, which dramatically provides abundant active sites and distinct charge transport pathway for organic pollutant oxidation. The S-scheme NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS heterojunction in the photo-Fenton-like system exhibited significantly enhanced degradation rate (0.15 min<sup>–1</sup>) at a low PMS dosage of 0.1 g/L, which is 19 times greater than that of the pristine NiS (0.0077 min<sup>–1</sup>). Density functional theory calculations confirmed that V<sub>O</sub> in NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS efficiently promoted PMS adsorption and lowered the energy barrier for electron transfer. Moreover, <em>in-situ</em> experiments and experimental evidence offer mechanistic insights into the PMS activation through photoexcitation, unraveling a dual-pathway activation mechanism involving reduction and oxidation processes over NiFe<sub>2</sub>O<sub>4–<em>x</em></sub>/NiS during the reaction. This work emphasizes the potential of vacancy engineering synergistic S-scheme heterojunction in developing efficient catalysts for regulating PMS activation, providing a promising solution the cost-effective and efficient treatment of organic wastewater.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 186-204"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532477","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)64839-X
Ziye Zheng , Yi Ren , Meng Dai , Hongsheng Li , Huizhen Cui , Sen Wang , Shuguang Wang , Zuoli He
Since conventional photocatalytic technology fails to achieve complete elimination of chlorophenol contaminants from aqueous environments, this study presents a synergistic photocatalysis-capacitive deionization (PC-CDI) system as an advanced solution for industrial chlorophenol wastewater remediation. The PC-CDI system, employing boron nitride/carbon nitride (BN/CN) heterojunction electrodes, demonstrates exceptional degradation performance toward chlorophenols. The high-surface-area porous BN/CN heterojunction facilitates electro-adsorption and charge carrier separation, thereby synergistically optimizing both photocatalytic (PC) and capacitive deionization (CDI) functionalities. Remarkably, the integrated system achieves a 2,4-DCP degradation efficiency of 97.15% and a 2,4,6-TCP degradation efficiency of 100% in 2 h. The CDI component enables spatial separation through the electro-adsorption of Cl– ions at the anode, effectively mitigating their interference and suppressing chlorinated byproduct formation. Concurrently, the electro-adsorption of positively charged chlorophenol pollutants accelerates their diffusion to catalytic sites, promoting the reactive oxygen species (ROS)-driven degradation of chlorophenol pollutants. The PC-CDI system exhibits robust stability (> 95% efficiency retention over five cycles) and broad applicability across various chlorophenol derivatives. By circumventing Cl–-induced side reactions and inhibiting chlorine radical generation during photocatalysis, this strategy minimizes the environmental risks associated with chlorinated byproducts during chlorophenol wastewater treatment. These findings establish the PC-CDI system as a sustainable and eco-friendly technology for industrial wastewater treatment.
{"title":"An eco-friendly photocatalytic coupling capacitive deionization system for efficient chlorophenol wastewater treatment","authors":"Ziye Zheng , Yi Ren , Meng Dai , Hongsheng Li , Huizhen Cui , Sen Wang , Shuguang Wang , Zuoli He","doi":"10.1016/S1872-2067(25)64839-X","DOIUrl":"10.1016/S1872-2067(25)64839-X","url":null,"abstract":"<div><div>Since conventional photocatalytic technology fails to achieve complete elimination of chlorophenol contaminants from aqueous environments, this study presents a synergistic photocatalysis-capacitive deionization (PC-CDI) system as an advanced solution for industrial chlorophenol wastewater remediation. The PC-CDI system, employing boron nitride/carbon nitride (BN/CN) heterojunction electrodes, demonstrates exceptional degradation performance toward chlorophenols. The high-surface-area porous BN/CN heterojunction facilitates electro-adsorption and charge carrier separation, thereby synergistically optimizing both photocatalytic (PC) and capacitive deionization (CDI) functionalities. Remarkably, the integrated system achieves a 2,4-DCP degradation efficiency of 97.15% and a 2,4,6-TCP degradation efficiency of 100% in 2 h. The CDI component enables spatial separation through the electro-adsorption of Cl<sup>–</sup> ions at the anode, effectively mitigating their interference and suppressing chlorinated byproduct formation. Concurrently, the electro-adsorption of positively charged chlorophenol pollutants accelerates their diffusion to catalytic sites, promoting the reactive oxygen species (ROS)-driven degradation of chlorophenol pollutants. The PC-CDI system exhibits robust stability (> 95% efficiency retention over five cycles) and broad applicability across various chlorophenol derivatives. By circumventing Cl<sup>–</sup>-induced side reactions and inhibiting chlorine radical generation during photocatalysis, this strategy minimizes the environmental risks associated with chlorinated byproducts during chlorophenol wastewater treatment. These findings establish the PC-CDI system as a sustainable and eco-friendly technology for industrial wastewater treatment.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 148-161"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532508","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)64828-5
Linhai He , Caiyi Lou , Lu Sun , Jing Niu , Shutao Xu , Yingxu Wei , Zhongmin Liu
Porous molecular sieve catalysts, including aluminosilicate zeolites and silicoaluminophosphate (SAPO) molecular sieves, have found widespread use in heterogeneous catalysis and are expected to play a key role in advancing carbon neutrality and sustainable development. Given the ubiquitous presence of water during catalyst synthesis, storage, and application, the interactions between water and molecular sieves as well as their consequent effects on frameworks and catalytic reactions have attracted considerable attention. These effects are inherently complex and highly dependent on various factors such as temperature, water phase, and partial pressure. In this review, we provide a comprehensive overview of the current understanding of water-molecular sieve interactions and their roles in catalysis, based on both experimental and theoretical calculation results. Special attention is paid to water-induced reversible and irreversible structural changes in aluminosilicate and SAPO frameworks at the atomic level, underscoring the dynamic and labile nature of these frameworks in water environments. The influence of water on catalytic performance and reaction kinetics in molecular sieve-catalyzed reactions is discussed from two perspectives: (1) its participation in reaction through hydrogen bonding interactions, such as competitive adsorption at active sites, stabilization of ground and transition states, and proton transfer bridge; (2) its role as a direct reactant forming new species via reactions with other guest molecules. Recent advancements in this area provide valuable insights for the rational design and optimization of catalysts for water-involved reactions.
{"title":"Water interactions in molecular sieve catalysis: Framework evolution and reaction modulation","authors":"Linhai He , Caiyi Lou , Lu Sun , Jing Niu , Shutao Xu , Yingxu Wei , Zhongmin Liu","doi":"10.1016/S1872-2067(25)64828-5","DOIUrl":"10.1016/S1872-2067(25)64828-5","url":null,"abstract":"<div><div>Porous molecular sieve catalysts, including aluminosilicate zeolites and silicoaluminophosphate (SAPO) molecular sieves, have found widespread use in heterogeneous catalysis and are expected to play a key role in advancing carbon neutrality and sustainable development. Given the ubiquitous presence of water during catalyst synthesis, storage, and application, the interactions between water and molecular sieves as well as their consequent effects on frameworks and catalytic reactions have attracted considerable attention. These effects are inherently complex and highly dependent on various factors such as temperature, water phase, and partial pressure. In this review, we provide a comprehensive overview of the current understanding of water-molecular sieve interactions and their roles in catalysis, based on both experimental and theoretical calculation results. Special attention is paid to water-induced reversible and irreversible structural changes in aluminosilicate and SAPO frameworks at the atomic level, underscoring the dynamic and labile nature of these frameworks in water environments. The influence of water on catalytic performance and reaction kinetics in molecular sieve-catalyzed reactions is discussed from two perspectives: (1) its participation in reaction through hydrogen bonding interactions, such as competitive adsorption at active sites, stabilization of ground and transition states, and proton transfer bridge; (2) its role as a direct reactant forming new species via reactions with other guest molecules. Recent advancements in this area provide valuable insights for the rational design and optimization of catalysts for water-involved reactions.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"79 ","pages":"Pages 9-31"},"PeriodicalIF":17.7,"publicationDate":"2025-11-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145532391","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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