Journal of Catalysis最新文献

{"title":"Interfacial effect of CoZn-MOFs synergizes with In doping to notably improve efficiency of TaON photoanode photoelectrochemical water splitting","authors":"Shaomang Wang ,&nbsp;Qiankun Deng ,&nbsp;Chengye Huang ,&nbsp;Zheng Shen ,&nbsp;Yuan Guan ,&nbsp;Zhongyu Li ,&nbsp;Shicheng Yan ,&nbsp;Zhigang Zou","doi":"10.1016/j.jcat.2025.116304","DOIUrl":"10.1016/j.jcat.2025.116304","url":null,"abstract":"<div><div>For photoelectrochemical hydrogen evolution by complete water splitting, the creation of strong and efficient photoanodes is essential. Herein, the In-TaON/CoZn-MOFs photoanode was developed by doping In ions into TaON, then compounded by CoZn-MOFs. The In-TaON/CoZn-MOFs exhibited remarkably improved performance after cyclic voltammetry (CV) treatment. The current density of In-TaON/CoZn-MOFs-CV was 2.63 mA cm⁻² at 1.23 V (vs RHE) under light irradiation (AM 1.5G), which was around 7.3 times that of TaON. After 10 h of running, the current density generated by In-TaON/CoZn-MOFs-CV could still reach about 2 mA cm⁻². Compared to the ΔF_max value of 1.77 eV for TaON, the ΔF_max value of In-TaON/<strong><em>Co</em></strong>Zn-MOFs with Co²⁺ as the active site was reduced to 0.38 eV. As a result, the In-TaON/CoZn-MOFs-CV produced a quantity of O₂ that was 17.7 times that of TaON.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116304"},"PeriodicalIF":6.5,"publicationDate":"2025-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144515282","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":"Co-promoter interactions within silver-catalyzed propylene epoxidation by molecular oxygen","authors":"Joseph Esposito,&nbsp;Aditya Bhan","doi":"10.1016/j.jcat.2025.116305","DOIUrl":"10.1016/j.jcat.2025.116305","url":null,"abstract":"<div><div>Propylene epoxidation on promoted Ag catalysts requires several promoters including gaseous co-feeds of allyl chloride (5–20 ppm), nitric oxide (100–1000 ppm), and carbon dioxide (2–10 vol%) on K-promoted Ag/CaCO₃. Steady-state rate and selectivity trends with respect to individual promoter concentrations reveal, in addition to direct influence of promoters on oxidation intermediates, co-promoters significantly alter the nature and magnitude of the effect of other co-promoters. On K-promoted Ag/CaCO₃, nitric oxide increases epoxidation selectivity at low concentrations (depending on K loading, up to ∼100 ppm NO) and decreases selectivity at higher concentrations (&gt;200 ppm NO). Co-promoting K concentrations significantly influence the concentrations of NO required for selective oxidation, evincing cooperative co-promotional effects of NO and K. At low levels of K/NO promotion, carbon dioxide (0.2–40 vol%) weakly inhibits O₂ activation rates (∼0.3 order inhibition) and inhibits selectivity while at high levels of K/NO promotion, co-fed CO₂ increases selectivity and reaches maximal order inhibition of rates (at ∼0.5 order inhibition). These results can be rationalized on the basis of selectivity-enhancing, competing alkali-stabilized NO_x and/or CO_x derived from co-fed NO and CO₂. NO renders half-order promotion of steady-state rates on K-promoted catalysts, and transient experiments show NO slowly generates long-lived surface intermediates relevant to catalytic activity for both oxidation and chlorination—consistent either with NO generating an activity-enhancing, co-catalytic NO_x intermediate or removing surface-poisoning, alkali-stabilized CO_x species to promote catalytic activity. K promotion (&gt;0.05 mol K (mol Ag_bulk)⁻¹) is also shown to substantially alter the promoting action of co-fed allyl chloride, with K-bare catalysts featuring significantly weaker selectivity promotion by the organochloride. Insights into co-promoter interactions suggest selective propylene epoxidation occurs only on active sites covered in appropriate concentrations of alkali-stabilized chlorine and oxyanions derived from CO₂ and NO_x.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116305"},"PeriodicalIF":6.5,"publicationDate":"2025-06-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144515281","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":"Pre-treated carbon additive enables reduction of metal loading in CoNiFe oxide-based OER electrocatalysts while maintaining performance","authors":"Trang Minh Pham,&nbsp;Na Liu,&nbsp;Stephan Bartling,&nbsp;Nils Rockstroh,&nbsp;Reinhard Eckelt,&nbsp;Wen Ju,&nbsp;Annette-Enrica Surkus,&nbsp;Robert Francke","doi":"10.1016/j.jcat.2025.116299","DOIUrl":"10.1016/j.jcat.2025.116299","url":null,"abstract":"<div><div>Mixed oxides (MO) of Co, Ni, and Fe have emerged as promising catalysts for the oxygen evolution reaction (OER) in alkaline water electrolysis (AWE). Although they are significantly cheaper than the precious metal catalysts used for proton exchange membrane (PEM) water splitting, the limited availability of Co and the exceptionally poor environmental footprint of Co and Ni mining remain challenges for scaling up AWE capacities. In this context, we present a promising approach toward reducing the metal content while preserving the catalytic performance. Based on a recent work on CoNiFeO_x OER catalysts from our group, admixture of pre-treated Vulcan carbon XC-72R (VC) at different synthesis stages in various loadings was evaluated in view of material structure and electrocatalytic activity. Attractive performance characteristics were obtained for the optimized MO-VC composite material, <em>e.g.</em>, a mass activity of 370 A <span><math><mrow><msubsup><mi>g</mi><mrow><mi>C</mi><mi>o</mi><mi>N</mi><mi>i</mi><mi>F</mi><mi>e</mi></mrow><mrow><mo>-</mo><mn>1</mn></mrow></msubsup></mrow></math></span> at 1.56 V vs. RHE and a Tafel slope of 39.0 mV dec⁻¹. Stable long-term performance under practical AWE conditions was confirmed in an anion exchange membrane (AEM) electrolyzer. An understanding of the effect of carbon admixture was achieved by combining <em>in situ</em> X-ray absorption spectroscopy, analysis of the electrochemically active surface area, as well as electrochemical impedance spectroscopy. The results point toward a benign impact of carbon admixture on the electronic structure of the MO domains under potential bias.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116299"},"PeriodicalIF":6.5,"publicationDate":"2025-06-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144515285","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":"Spatiotemporal investigation of the regeneration of a shaped zeolite catalyst extrudate using operando powder X-ray diffraction computed tomography","authors":"Izar Capel Berdiell ,&nbsp;Lars F. Lundegaard ,&nbsp;Pablo Beato ,&nbsp;Marco Di Michiel ,&nbsp;David S. Wragg ,&nbsp;Stian Svelle","doi":"10.1016/j.jcat.2025.116300","DOIUrl":"10.1016/j.jcat.2025.116300","url":null,"abstract":"<div><div>We have used <em>operando</em> powder X-ray diffraction computed tomography (PXRD-CT) analysed by parametric Rietveld refinements to monitor the regeneration of a deactivated ZSM-5 zeolite based extrudate employed as a catalyst in the methanol-to-hydrocarbon reaction. This investigation thus advances beyond previous studies of pure, powdered zeolites. We follow the coke oxidation by monitoring three XRD based descriptors. Lattice relaxation, monitored as the difference in length of the <em>a</em>- and <em>b</em>-lattice parameters (<em>a-b</em>), occurs first at the core of the extrudate and progresses towards the outer surface. This demonstrates a radial distribution of different coke species, wherein the heaviest, more oxidation resistant coke is matured near the external surface of the extrudate. In contrast, the total <em>non-framework species mass</em> (<em>NFSM</em>) decreased more uniformly throughout the extrudate, suggesting that chemical transformations of the coke species can occur prior to full oxidation. This notion is supported by in situ temperature programmed oxidation, which demonstrates that the regeneration of the ZSM-5/binder composite occurs in two distinct steps. We also observe that irreversible (hydro)thermal damage occurs in the severely coked regions of the extrudate during regeneration. Additionally, we demonstrate that the three different XRD based descriptors carry slightly different and complementary information. The (<em>a-b</em>) descriptor describes lattice distortion induced by rigid coke species. The total <em>non-framework species mass</em> (<em>NFSM</em>) and the <em>unit cell volume (UCV)</em>, in contrast, capture all guest species, including volatile compounds and water. However, as a drawback, the <em>UCV</em> is strongly influenced also by thermal effects, whereas the (<em>NFSM</em>) is virtually unaffected by temperature.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116300"},"PeriodicalIF":6.5,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144479634","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":"Facile preparation of alkali metal-doped Ru/MgO catalysts for ammonia decomposition via one-pot dry ball milling: structural and electronic promoting effect of K, Rb, and Cs","authors":"Hongyang Huang,&nbsp;Haifan Deng,&nbsp;Yuyin Ji,&nbsp;Dalin Li,&nbsp;Chongqi Chen,&nbsp;Huihuang Fang,&nbsp;Yu Luo,&nbsp;Lilong Jiang","doi":"10.1016/j.jcat.2025.116298","DOIUrl":"10.1016/j.jcat.2025.116298","url":null,"abstract":"<div><div>Ammonia decomposition is a promising method for on-site hydrogen generation for fuel cells. Ruthenium is the most active catalyst for this process, and modulation of its geometric and electronic properties is essential for achieving high catalytic performance. This study developed a facile approach for synthesizing alkali metal-doped Ru/MgO catalysts using a one-pot dry ball milling method with acetates as precursors. Characterization results indicate that K, Rb, and Cs act as effective structural and electronic promoters. Notably, the presence of alkali metals significantly inhibits the aggregation of bulk-like RuO₂, leading to the formation of well-dispersed RuO<em>_x</em>, which, upon reduction, produces small Ru nanoparticles. The average Ru particle size is about 2–3 nm, aligning with the theoretical optimal size for maximizing B₅ sites. XAS and DRIFTS analyses confirm that Ru species are stabilized due to the strong metal-promoter interaction between ruthenium and alkali metals via oxygen bonding. The resulting alkali metal-promoted Ru nanoparticles exhibit superior low-temperature activity for ammonia decomposition. The 2 K-3 %Ru/MgO catalyst achieves a high reaction rate of 11.5 mmol-NH₃ g_cat⁻¹ min⁻¹ at 400 °C under 30,000 mL g_cat⁻¹ h⁻¹, demonstrating one of the highest performances among Ru catalysts. Furthermore, this catalyst maintains high activity at 475 °C for 50 h without significant deactivation. The enhanced catalytic performance is attributed to the structural and electronic promotion effects of alkali metals, which facilitate the formation of B₅ site-rich and electron-rich Ru nanoparticles. These findings offer valuable insights into the role of alkali metals and provide helpful guidance for designing efficient alkali metal-promoted ruthenium catalysts for practical applications.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116298"},"PeriodicalIF":6.5,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144488568","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":"Montmorillonite-mediated cobalt-doped Fe-MOF composites: a route to efficient photo-driven benzene hydroxylation","authors":"Xu Jia ,&nbsp;Jiaqi Zhang ,&nbsp;Jiaolong Qiao ,&nbsp;Zhiqi Song ,&nbsp;Xuetong Xu ,&nbsp;Liuxue Zhang ,&nbsp;Xiulian Wang ,&nbsp;Genxing Zhu ,&nbsp;Shuyan Jiao","doi":"10.1016/j.jcat.2025.116297","DOIUrl":"10.1016/j.jcat.2025.116297","url":null,"abstract":"<div><div>In order to improve the efficiency of photocatalyst in the process of hydroxylation of benzene to phenol, a novel heterojunction material Fe-Co-MOFs/2D-MMT was prepared by in-situ composite technique. The modification strategy of cobalt-doping and montmorillonite-support effectively improves the photocatalytic performance of the material. The photocatalytic results demonstrated that the catalyst displayed the ability to catalyze the direct hydroxylation of benzene to phenol, achieving a yield of 30.06 % and a selectivity of 85.73 % under the optimal reaction conditions. And the composite showed excellent stability and efficiency in the photocatalytic process, which provided a new route for the application of modified MOFs in the hydroxylation of benzene to phenol.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116297"},"PeriodicalIF":6.5,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144488566","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":"Catalytic utilization of transition, post-transition and rare earth metal-substituted brownmillerite-related solids for the continuous-flow hydrogenations of CO2 and furfural into synthetic fuels","authors":"Rebeka Mészáros ,&nbsp;Adél Anna Ádám ,&nbsp;Kornélia Baán ,&nbsp;Ádám Pitó ,&nbsp;Gyula Halasi ,&nbsp;János Kiss ,&nbsp;András Sápi ,&nbsp;Zoltán Kónya ,&nbsp;Ákos Kukovecz ,&nbsp;Márton Szabados","doi":"10.1016/j.jcat.2025.116282","DOIUrl":"10.1016/j.jcat.2025.116282","url":null,"abstract":"<div><div>Brownmillerite-type perovskites (or called dicalcium ferrite derivatives, Ca₂Fe_1.4M_0.6O_x), as excellent candidates for Earth-abundant catalysts, were tested in gas- (CO₂) and liquid-phase (furfural) hydrogenations for the first time. Preparation of precursor forms of catalysts using a variety of metals M(III) = Al, Sc, Cr, Mn, Fe, Co, Ga, Y, Rh, Sb, In, La, Yb and Bi was attempted, and the results show that incorporation of metals larger than Sc(III) was not possible without the formation of extralattice phases. Dicalcium ferrite derivatives formed by calcination of hydrocalumite-based layered double hydroxides, interestingly, the appearance of the layered double hydroxides correlated well with the successful formation of brownmillerites in most cases. <em>In situ</em> reduced forms (containing Fe(0) and iron carbide active phases) of most materials performed well with and without impregnation of nickel nanoparticles in thermocatalytic CO₂ reduction. High CO selectivities between 60 and 99 % were measured, resulting from the combination of the following reaction pathways: hydrogen-assisted CO₂ dissociation, thermal decomposition of formyl and formate intermediates and reverse water gas shift reactions of carboxylate products. <em>Ex situ</em> reduced brownmillerites (or even hydrocalumites) with M = Fe and Rh possessed outstanding and robust activity in furfural reduction (by simultaneous direct and transfer hydrogenation), and furfuryl alcohol selectivity was consistently full in the scale-up tests. In these hydrogenations to sustainable fuels, performance of brownmillerite-based catalysts has been able to outperform many of the transition (Co, Ni, Cu) and noble metal (Ru, Pd, Pt) catalysts known from the literature, highlighting the potential of these cheap and readily producible materials.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116282"},"PeriodicalIF":6.5,"publicationDate":"2025-06-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144479635","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":"Work-function-mediated unidirectional charge flow enables 139-fold enhanced photocatalytic hydrogen evolution on g-C3N4","authors":"Yiming Zhang ,&nbsp;Yunpeng Zhang ,&nbsp;Jingang Yang ,&nbsp;Chenchen Feng ,&nbsp;Shibo Shao ,&nbsp;Peisen Li ,&nbsp;Qizheng Dong ,&nbsp;Xusheng Wang","doi":"10.1016/j.jcat.2025.116296","DOIUrl":"10.1016/j.jcat.2025.116296","url":null,"abstract":"<div><div>Suppressing photogenerated carrier recombination remains a pivotal challenge in photocatalyst design. In this work, we strategically integrate Co₃O₄ as a hole-extracting layer and Ni as an electron-trapping cocatalyst onto graphitic carbon nitride (g-C₃N₄), establishing a work-function-gradient-driven charge transport pathway along the Co₃O₄ → g-C₃N₄ → Ni directional cascade, resulting enhanced carrier concentration and charge migration kinetics. The optimized 1.5 %Ni-1 %Co₃O₄-C₃N₄ achieves a remarkable photocatalytic hydrogen evolution rate of 16.71 μmol h⁻¹, surpassing 1 %Co₃O₄-C₃N₄ (5.17 μmol h⁻¹), 1.5 %Ni-C₃N₄ (1.64 μmol h⁻¹) and g-C₃N₄ (0.12 μmol h⁻¹) by 3.2, 10.2 and 139.2 times, with robust stability over multiple cycles. Photoelectric characterizations confirm accelerated charge separation via synergistic electron transfer by Ni electron sinks and Co₃O₄ hole extractor. Density functional theory reveals work function gradient of Co₃O₄, g-C₃N₄, and Ni driving unidirectional electron flow from Co₃O₄ to Ni active sites via g-C₃N₄ as bridge, while an upward-shifted Ni d-band center and optimized hydrogen adsorption energy (ΔG_*H) of 1.5 %Ni-1 %Co₃O₄-C₃N₄ enhance *H reduction kinetics. This work establishes a work-function-gradient based strategy for advancing solar-to-hydrogen conversion technologies.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116296"},"PeriodicalIF":6.5,"publicationDate":"2025-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144371203","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":"Mechanistic insights into nitrate electroreduction on CuNi alloys: d-band center modulation of key intermediates","authors":"Qiuling Jiang ,&nbsp;Ying Wang ,&nbsp;Zhijian Wu","doi":"10.1016/j.jcat.2025.116287","DOIUrl":"10.1016/j.jcat.2025.116287","url":null,"abstract":"<div><div>Electrochemical nitrate reduction reaction to ammonia (NO₃RR) is a promising alternative to the traditional Haber-Bosch process for NH₃ synthesis. The development of efficient electrocatalysts is crucial for this process. Copper-nickel alloy (CuNi) catalysts demonstrate excellent catalytic performance over pristine copper (Cu) and pristine nickel (Ni) catalysts, and it is noted that Ni incorporation significantly improves nitrate removal efficiency while suppressing undesirable nitrite formation for NO₃RR. However, the reaction mechanism of NO₃RR on CuNi catalysts remains unclear, particularly regarding the role of Ni incorporation. In this study, constant-potential method calculations were applied to CuNi(1 1 1) catalysts (Cu₃Ni₁(1 1 1), Cu₂Ni₂(1 1 1), and Cu₁Ni₃(1 1 1) with Cu:Ni atomic ratios of 3:1, 1:1, and 1:3, respectively) to understand their enhanced NO₃RR performance compared to pristine Cu(1 1 1) and pristine Ni(1 1 1) catalysts. The potential-dependent adsorption energetics reveal the enhanced co-adsorption of NO₃* and H* facilitates nitrate deoxidation-protonation and improves Faradic efficiency, while the strengthened NO₂* binding simultaneously promotes its further reduction rather than desorption. Microkinetic analyses identify the dominant surface intermediates, and the simulated NH₃ formation current densities exhibit highly consistent with experimental trends. Furthermore, the electronic structure analyses elucidate that the <em>d</em>-band center, optimized near Cu:Ni = 1:1, modulates the binding strengths of key intermediates and reduces activation barriers, thereby suppressing nitrite formation while promoting selective ammonia formation. These fundamental insights not only rationalize previously reported experimental phenomena but also provide design principles for developing efficient NO₃RR electrocatalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116287"},"PeriodicalIF":6.5,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144371204","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":"Electrochemical CO2 reduction by Mn-mesbpy complex: Tuning redox properties and mechanistic switching via ligand substitution","authors":"Miho Isegawa","doi":"10.1016/j.jcat.2025.116290","DOIUrl":"10.1016/j.jcat.2025.116290","url":null,"abstract":"<div><div>Density functional theory (DFT) calculations were used to investigate the effects of electron-donating and electron-withdrawing substituents on the mesbpy ligand of Mn-based complexes employed in the electrochemical reduction of CO₂. The influence of these substituents on reduction potentials, CO₂ binding affinities, and the overall catalytic mechanism was systematically examined. DFT results indicated that Mn complexes bearing electron-donating groups (–CH₃, –OH), neutral groups (–H), and moderately electron-withdrawing groups (–F) can bind CO₂ in the two-electron-reduced state. In contrast, Mn complexes with strongly electron-withdrawing substituents (–CF₃, –CN) facilitate the initial reduction step but fail to bind CO₂ at the same redox state, thus requiring a third electron for activation. However, these complexes become energetically inefficient as catalysts due to the high energy demand associated with the three-electron reduction. The mechanistic insights presented here, which distinguish Mn complexes bearing electron-donating or moderately electron-withdrawing substituents from those with strongly electron-withdrawing groups, provide valuable design principles for the development of energy-efficient Mn-based CO₂ reduction catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116290"},"PeriodicalIF":6.5,"publicationDate":"2025-06-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144371253","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}