Lixue Zhang , Guoyu Cheng , Fabin Zhou , Xin Yang , Huicheng Cheng , Mei Yu , Dahong Jiang , Peng Zhou , He Yang , Bingxin Yuan , Wenjun Tang , Ji-cheng Shi
{"title":"The terphenyl phosphine TRuPhos: a novel and efficient ligand for the palladium-catalyzed arylation of hindered primary alkyl amines with mechanism clarification","authors":"Lixue Zhang , Guoyu Cheng , Fabin Zhou , Xin Yang , Huicheng Cheng , Mei Yu , Dahong Jiang , Peng Zhou , He Yang , Bingxin Yuan , Wenjun Tang , Ji-cheng Shi","doi":"10.1016/j.jcat.2025.116391","DOIUrl":"10.1016/j.jcat.2025.116391","url":null,"abstract":"<div><div>Terphenyl phosphines are rising as powerful supporting ligands in the palladium-catalyzed C-N cross-coupling reactions, leading to reduced catalyst loadings and broadened substrate scope. To extend the terphenyl phosphine family, TRuPhos and TSPhos along with their 2-amino-biphenyl-ƞ<sup>2</sup>-C,N palladium precatalysts have been synthesized and characterized, including one complex by single-crystal diffraction. TRuPhos exhibits unprecedented efficiency in the palladium-catalyzed arylation of many hindered primary alkyl amines. Mechanism studies have clarified that: 1) the transmetalation <strong>path A</strong> involving amine adducts of oxidative addition product does not work by the TRuPhos-supported palladium catalyst in the arylation of hindered primary alkyl amines, but works for that in small bulk amines; 2) the <strong>path C</strong> involving the substitution of halogen atoms on oxidative addition products by <em>t</em>BuO groups seems impossible as well; 3) the reaction occurred between oxidative addition products and sodium amides forming C-N coupling products suggests that <strong>path B</strong> is a possible transmetalation pathway in Pd/TRuPhos-catalyzed arylation of hindered primary alkyl amines.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116391"},"PeriodicalIF":6.5,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144910684","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}
Yuhao Yang , Jie Ran , Teng Wang , Yongning Ma , Junli Zhu , Xiaolong Li , Zhuoya Zhao
{"title":"Enhanced hydrogen production performance and stability simultaneously in aqueous-phase reforming of methanol over Pt/V2O3-V8C7 based on strong-weak metal support interactions","authors":"Yuhao Yang , Jie Ran , Teng Wang , Yongning Ma , Junli Zhu , Xiaolong Li , Zhuoya Zhao","doi":"10.1016/j.jcat.2025.116397","DOIUrl":"10.1016/j.jcat.2025.116397","url":null,"abstract":"<div><div>Aqueous phase reforming of methanol (APRM) is an effective method for the storage and transportation of hydrogen (H<sub>2</sub>). However, this approach faces challenges due to the limited activity and stability of metal-supported catalysts. In this study, Pt/V<sub>2</sub>O<sub>3</sub>-V<sub>8</sub>C<sub>7</sub> metal-supported catalysts were prepared for APRM and the H<sub>2</sub> production of Pt/V<sub>2</sub>O<sub>3</sub>-V<sub>8</sub>C<sub>7</sub> at 200 °C was 96.52 mmol·g<sup>−1</sup>·h<sup>−1</sup>, which is 1.83 times and 1.71 times higher than the H<sub>2</sub> production performance of Pt/V<sub>2</sub>O<sub>3</sub> and Pt/V<sub>8</sub>C<sub>7</sub>, respectively. Moreover, the catalyst demonstrated remarkable stability after 10 in situ cycling tests. Structural characterization revealed that there is a strong metal-support interaction (SMSI) between Pt and V<sub>8</sub>C<sub>7</sub>, and a weak metal-support interaction (WMSI) between Pt and V<sub>2</sub>O<sub>3</sub>, which inhibits the sintering of Pt on the metal-supported catalyst. Furthermore, a straightforward experimental method has been developed that enables accurate inference of the catalytic reaction mechanism in APRM without the need for in situ material characterization. The reaction mechanism indicates that the Pt-V<sub>8</sub>C<sub>7</sub> interface serves as the active site for the methanol decomposition step, while the surface of V<sub>2</sub>O<sub>3</sub> acts as the active site for the water–gas shift reaction step. This strategy of strong–weak MSI offers a novel approach to enhancing both the stability and H<sub>2</sub> production performance in APRM.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"452 ","pages":"Article 116397"},"PeriodicalIF":6.5,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144905974","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}
Shan Ding , Yu-Ting Hui , Qingfeng Wei , Guang-Sheng Yang , Zhe Tang , Shi-Qi Wang , Xinning Zhang , Yi-Jia Wang , Chunjie Jiang
{"title":"Carbazolyl-based metal organic framework for photocatalytic antibiotic degradation and H2O2 green generation assisted by silver nanoparticles","authors":"Shan Ding , Yu-Ting Hui , Qingfeng Wei , Guang-Sheng Yang , Zhe Tang , Shi-Qi Wang , Xinning Zhang , Yi-Jia Wang , Chunjie Jiang","doi":"10.1016/j.jcat.2025.116401","DOIUrl":"10.1016/j.jcat.2025.116401","url":null,"abstract":"<div><div>Tetracycline, a widely used antibiotic that persists in the environment, is a significant pollutant, making its efficient degradation crucial for ecosystem and human health. Meanwhile, green production of hydrogen peroxide, an important chemical raw material and green oxidant, is significant in various fields. In this study, a novel visible-light-responsive photocatalyst, the ACM-X series material, was successfully synthesized through post-synthetic modification of Cz-MOF-2, with the deposition of Ag nanoparticles on the surface significantly enhancing the photocatalytic performance, enabling efficient degradation of tetracycline (TC) and high-yield production of hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) under simulated solar light irradiation. The Ag surface plasmon resonance (SPR) effect played a crucial role in improving charge separation efficiency, as confirmed by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), and electrochemical measurements. The ACM-1 catalyst demonstrated exceptional photocatalytic activity, achieving over 95 % TC degradation within 60 min and a H<sub>2</sub>O<sub>2</sub> production rate of 50 μmol/h. The free radical scavenging experiments and electron paramagnetic resonance (EPR) technique confirmed that reactive oxygen species (ROS), including superoxide anion radicals (·O<sub>2</sub><sup>−</sup>), hydroxyl radicals (·OH) and singlet oxygen (<sup>1</sup>O<sub>2</sub>), were identified as key intermediates in the photocatalytic process. Density functional theory (DFT) calculations revealed that Ag modification reduced the band gap of Cz-MOF-2, enhancing light absorption and promoting electron transfer. The 2e<sup>−</sup> oxygen reduction reaction (ORR) for H<sub>2</sub>O<sub>2</sub> production was found to be spontaneous, with Ag acting as an electron and proton transfer mediator. Additionally, the degradation pathway of tetracycline (TC) was elucidated by using a mass spectrometer. The ACM − 1 catalyst exhibited excellent stability and reusability during multiple cycles of use, highlighting its potential in environmental remediation and sustainable chemical synthesis. This work provides a promising strategy for the design of advanced photocatalysts for solar energy conversion and pollutant degradation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116401"},"PeriodicalIF":6.5,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906336","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}
Angela Nguyen , Griffin A. Canning , Robert M. Rioux , Michael J. Janik
{"title":"A Markov chain Monte Carlo (MCMC) Bayesian inference approach to analyze apparent activation barriers and reaction orders from microreactor data","authors":"Angela Nguyen , Griffin A. Canning , Robert M. Rioux , Michael J. Janik","doi":"10.1016/j.jcat.2025.116389","DOIUrl":"10.1016/j.jcat.2025.116389","url":null,"abstract":"<div><div>Statistical analysis of steady-state catalytic kinetic data is often limited by data sparsity due to the slow pace at which the data is collected. Data sparsity and limitations in statistical analysis make it difficult to differentiate between mechanistic models and catalytic sites. A Bayesian inference tool is reported for catalysis researchers to estimate error in the determination of reaction orders from steady state microreactor data. The benefits of a Bayesian inference approach are discussed, as an alternative to the more common frequentist approach. The approach incorporates prior knowledge of the system and the data collected to form an error estimate on reaction orders. We investigated the effects of three distinct data treatments—individual fitting of trials, pooled analysis, and constrained regression methods—on the precision and uncertainty of reaction order determinations. To assess the robustness of our findings, we conducted sensitivity analyses to evaluate the influence of Bayesian parameters on uncertainty estimation. Additionally, we utilized synthetic data to illustrate how data quality impacts the precision of uncertainty assessments. We show Bayesian analysis can obtain a more precise estimation of error with a sparse data set than a frequentist analysis. This work provides strong evidence that the adoption of Bayesian analysis of kinetic data may help researchers make more precise arguments as to the strength of their evidence for a particular mechanistic hypothesis, or in comparing across different catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116389"},"PeriodicalIF":6.5,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901470","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}
{"title":"Hydrodenitrogenation of alkylamines over supported Ru-based catalysts","authors":"Momoka Hikime , Yoshinao Nakagawa , Kei Sato , Mizuho Yabushita , Keiichi Tomishige","doi":"10.1016/j.jcat.2025.116390","DOIUrl":"10.1016/j.jcat.2025.116390","url":null,"abstract":"<div><div>Hydrodenitrogenation (HDN) of 1-cyclohexylethylamine to ethylcyclohexane was investigated with various Ru-based catalysts. Ru-Ir/α-Al<sub>2</sub>O<sub>3</sub> (1 wt% Ru, 4 wt% Ir) catalyst was found to be superior to other supported Ru catalysts in terms of activity and selectivity to ethylcyclohexane. Characterization with XRD, TEM-EDX and XAFS showed that uniform Ru-Ir alloy particles of approximately 4 nm in size were formed on α-Al<sub>2</sub>O<sub>3</sub>. The optimal Ru-Ir/α-Al<sub>2</sub>O<sub>3</sub> catalyst gave 94 % yield of ethylcyclohexane. The time-course results and the reaction results of bis-(1-cyclohexylethyl)-amine (coupled compound of the substrate) demonstrated that the direct C<img>N cleavage route and indirect route via the coupled compound both proceeded in the HDN of 1-cyclohexylethylamine. The propylamine-TPD results with H<sub>2</sub> treatment after the adsorption of propylamine on the catalyst suggested that the adsorption of H<sub>2</sub> and amine was favorable on the Ru and Ir species, respectively. The catalyst was reusable after washing with ethanol with a slight loss of activity. The catalyst was also effective for the HDN reaction of other amines, and the HDN of some substrates proceeded mainly in the indirect route via the coupled compound.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116390"},"PeriodicalIF":6.5,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901469","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}
{"title":"Cooperative phase-separated Cu–Zn catalyst for selective CO2 electrochemical reduction toward ethanol: theoretical insights into the role of the interface sites","authors":"Athis Watwiangkham , Jirapat Santatiwongchai , Arisa Kaewpratum , Lappawat Ngamwongwan , Tongjai Chookajorn , Suwit Suthirakun , Pussana Hirunsit","doi":"10.1016/j.jcat.2025.116393","DOIUrl":"10.1016/j.jcat.2025.116393","url":null,"abstract":"<div><div>Bimetallic Cu–Zn electrocatalysts have emerged as promising candidates for selectively reducing carbon dioxide (CO<sub>2</sub>) to ethanol. While CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) has been studied extensively on monometallic Cu and Zn catalysts and their homogenous alloys, the influence of heterogeneous Cu–Zn interfaces remain underexplored. Herein, we used density functional theory (DFT) calculations to investigate the interface effects of phase-separated Cu–Zn catalysts on CO<sub>2</sub>RR toward ethanol. Interface sites significantly modulate intermediate stability and enhance the C–C coupling step, particularly CO–CH coupling, which is both thermodynamically and kinetically favorable (Δ<em>G</em><sub>rxn</sub> = −1.28 eV; Δ<em>G</em><sup>‡</sup> = 0.27 eV). Interface site favors the ethanol pathway over ethylene after subsequent *CHCO formation. Microkinetic analysis further suggests that CO–CH coupling dominantly contributes to the ethanol production. These findings reveal the cooperative role of interface sites in enabling selective ethanol production, providing insights into the rational design of Cu–Zn electrocatalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116393"},"PeriodicalIF":6.5,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901472","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}
Ya-Nan Wang , Xinghua Wang , Shihan Liu , Lin Zhang , Xin Dai , Ruopeng Bai , Shi-Jun Li , Yu Lan
{"title":"DFT study on multi-carbonylation in a valence-switchable model","authors":"Ya-Nan Wang , Xinghua Wang , Shihan Liu , Lin Zhang , Xin Dai , Ruopeng Bai , Shi-Jun Li , Yu Lan","doi":"10.1016/j.jcat.2025.116398","DOIUrl":"10.1016/j.jcat.2025.116398","url":null,"abstract":"<div><div>This report describes a transition metal-catalyzed switchable carbonylation model that enables selective carbonylation reactions. Mono-/dicarbonylation reactions catalyzed by copper(I) are investigated to validate the proposed model. Mechanistic studies indicate that a low-valent metal center captures a CO molecule to afford the corresponding metal-acyl species. Then, the alkyl bromide, with a weak oxidation potential, reacts with the metal-acyl species via halogen atom transfer, which generates an acyl radical species, leading to the dicarbonylation product. Alternatively, in the presence of alkyl iodide, which has a stronger oxidation potential, the low-valent metal center is preferentially oxidized to higher valence, with concomitant generation of only the monocarbonylation product. Finally, energy decomposition analysis based on absolutely localized molecular orbitals and variational forward–backward analysis reveals the origin of the observed chemoselectivity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116398"},"PeriodicalIF":6.5,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901477","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}
Yong Wang , Yongkang Sun , Tingting Wang , Fusheng Huang , Tianyi Cheng , Zhongpeng Li , Jianqiang Zhu , Jichang Liu , Bin Dai , Jiangbing Li , Xuhong Guo
{"title":"‘N-Defective MOF-derived ZnCuBi catalysts with Zn-N sites: Stabilizing Cu+/Cu0 active interfaces for efficient formaldehyde ethynylation to 1,4-butynediol","authors":"Yong Wang , Yongkang Sun , Tingting Wang , Fusheng Huang , Tianyi Cheng , Zhongpeng Li , Jianqiang Zhu , Jichang Liu , Bin Dai , Jiangbing Li , Xuhong Guo","doi":"10.1016/j.jcat.2025.116395","DOIUrl":"10.1016/j.jcat.2025.116395","url":null,"abstract":"<div><div>The development of efficient catalysts under reducing atmospheres remains a significant challenge. In this study, a series of ZnCuBi catalysts were synthesized by incorporating nitrogen defect sites into a porous carbon–nitrogen network while constructing Zn-N active sites and Cu<sup>+</sup>/Cu<sup>0</sup> active interfaces (ZnCuBi-N<sub>v</sub>C). Polyvinylpyrrolidone (PVP) modified ZnBiCu-BTC (PVP@ZnBiCu-BTC) served as a precursor, with polyvinylpyrrolidone acting as a nitrogen source during catalyst preparation. The incorporation of Bi enhanced the dispersion of Cu and Zn species. Synergistic catalytic behaviour was demonstrated through experimental characterization and DFT calculations. The Zn-N structure significantly enhanced the adsorption and activation of formaldehyde, while interfacial interactions between copper species promoted acetylene activation. The N-defect structure also facilitated electron transfer, stabilizing the Cu<sup>+</sup>/Cu<sup>0</sup> active interface. The ZnCuBi-N<sub>v</sub>C catalyst exhibited 95 % selectivity for 1,4-butanediol (BD) in a cyclic activity test under a reducing atmosphere containing acetylene and formaldehyde.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116395"},"PeriodicalIF":6.5,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901475","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}
Yuetan Su , Chunyao Fang , Sihang Liu , Ang Cao , Jianhua Yan
{"title":"Is the N2 dissociative mechanism universal across stepped metal surfaces for ammonia synthesis?","authors":"Yuetan Su , Chunyao Fang , Sihang Liu , Ang Cao , Jianhua Yan","doi":"10.1016/j.jcat.2025.116394","DOIUrl":"10.1016/j.jcat.2025.116394","url":null,"abstract":"<div><div>The need of more efficient catalysts for thermal ammonia synthesis is urgent as ever, but is limited by the absence of innovative mechanisms beyond traditional dissociative mechanism. Recently, however, the associative mechanism has emerged as a viable route especially in electro-catalysis, calling for a deeper understanding in its possibility in catalyst design for thermal process. Here, we conduct a comprehensive analysis of elementary reactions on stepped metal surfaces, establishing scaling relationships for the associative mechanism and refining the ammonia synthesis volcano plot. Our results reveal that under typical reaction conditions (473–773 K, 1–100 bar), metal surfaces such as Ru, Fe, and Rh predominantly follow the dissociative mechanism with high reaction rates, while Mo, Ni, Pd, and Cu favor the associative mechanism but exhibit lower reaction rates. Expanding these finding through volcano plots to 21 metal surfaces, we observed that pure metal surfaces do not fall into the high-activity region for associative hydrogenation due to the scaling relationships. Therefore, we identify the N<sub>2</sub> direct hydrogenation step of N–HN bond formation as a key descriptor among the numerous elementary reaction steps of associative mechanism, and the efficiency of the associative pathway can be significantly enhanced by lowering the energy barrier of this step-particularly by breaking the linear scaling relationships. These findings challenge the traditional view of stepped metal surfaces favor dissociative mechanisms, and provide a new paradigm for catalysts design by reinventing reaction mechanisms.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116394"},"PeriodicalIF":6.5,"publicationDate":"2025-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901473","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}
Qi Chen , Xingxing Huang , Cheng Liu , Yueling Chen , Jionghua Wu , Jimmy C. Yu , Ling Wu
{"title":"MoS2 nanoparticles/MIL-100(Fe) heterojunction with Type II interfacial charge transfer for efficient photocatalytic nitrogen reduction","authors":"Qi Chen , Xingxing Huang , Cheng Liu , Yueling Chen , Jionghua Wu , Jimmy C. Yu , Ling Wu","doi":"10.1016/j.jcat.2025.116386","DOIUrl":"10.1016/j.jcat.2025.116386","url":null,"abstract":"<div><div>The attainment of rapid charge mobility and effective N<sub>2</sub> activation is of critical importance for photocatalytic nitrogen fixation but it has always been a challenge. Such challenge may be met by the construction of a Type II MoS<sub>2</sub> nanoparticles/ MIL-100(Fe) heterojunction photocatalyst. The new material possesses charge migration channels that facilitate the separation of photogenerated carriers. This charge redistribution during photocatalysis is confirmed by experimental results showing a decrease of charge density on the Fe species and an increase of that on Mo. Moreover, DFT calculations show that the adsorption of N<sub>2</sub> and H<sub>2</sub>O is more likely to occur on Fe sites and Mo sites, respectively. These findings clearly suggest a drastically improved spatial isolation of reduction and oxidation sites on the photocatalyst as compared to pristine MIL-100(Fe). The optimized MoS<sub>2</sub>/MIL-100(Fe) exhibits a NH<sub>4</sub><sup>+</sup> yield rate of 1.29 μmol·h<sup>−1</sup> as excellent utilization of photoinduced electron-hole pairs and effective adsorption and activation of N<sub>2</sub> become possible. This work offers an insight on the synergy of heterojunction engineering with coordinated activation for photocatalytic ammonia synthesis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"451 ","pages":"Article 116386"},"PeriodicalIF":6.5,"publicationDate":"2025-08-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901545","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}