Journal of Catalysis最新文献

{"title":"First-principles, data-guided screening and catalyst design: Unveiling energetic trade-offs in ammonia decomposition","authors":"Yuna Song ,&nbsp;Yanggeun Ju ,&nbsp;Chaerin Son ,&nbsp;Dasol Bae ,&nbsp;You Jin Go ,&nbsp;Sung Bong Kang ,&nbsp;Minkyu Kim","doi":"10.1016/j.jcat.2025.116339","DOIUrl":"10.1016/j.jcat.2025.116339","url":null,"abstract":"<div><div>Ammonia decomposition is a promising route for CO₂-free hydrogen production, but the development of efficient and cost-effective catalysts remains a challenge. Here, we employed a dual approach combining computational screening and free energy analysis to identify optimal catalysts, which were then validated experimentally. Pearson correlation coefficient analysis revealed a volcano-type relationship between NH₃ dissociation energy (E_diss,NH3) and N₂ adsorption energy (E_ad,N2), highlighting Ru as the most effective monometallic catalyst. Reactor tests using supported Ru, Rh, Ir, Ni, and Co catalysts confirmed these predictions, with Ru exhibiting the highest NH₃ conversion and a strong correlation between turnover frequency, activation energy (E_a), and electronic descriptors. Using this validated approach, we extended our analysis to bimetallic systems, identifying Ru-Ni alloys, as a promising alternative with balanced NH₃ activation and N₂ desorption. These findings demonstrate the effectiveness of combining computational and experimental methods to design high-performance NH₃ decomposition catalysts. Further refinement of Ru-Ni alloy synthesis and structural control could enhance catalytic activity, supporting scalable hydrogen production.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116339"},"PeriodicalIF":6.5,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144748101","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":"Structural effects of thiolated silsesquioxane ligands on the stabilization of gold nanoparticles: Implications for the catalytic dehydrogenation of alcohols","authors":"Kodai Ito ,&nbsp;Yujia Liu ,&nbsp;Anh Ngoc Thai ,&nbsp;Momoko Takahashi ,&nbsp;Kyoka Koizumi ,&nbsp;Niyaz Yagafarov ,&nbsp;Eddy Petit ,&nbsp;Saad Sene ,&nbsp;Joulia Larionova ,&nbsp;Yannick Guari ,&nbsp;Masafumi Unno ,&nbsp;Armelle Ouali","doi":"10.1016/j.jcat.2025.116342","DOIUrl":"10.1016/j.jcat.2025.116342","url":null,"abstract":"<div><div>One of the main challenges in nanoparticle-promoted catalysis is preventing sintering under reaction conditions, while maintaining both stability and high catalytic activity − properties tunable via rational surface ligand design. Although molecular silsesquioxanes offer structural versatility and robustness, their use as stabilizing agents for gold nanoparticles remains underexplored, particularly regarding their influence on nanoparticle properties and catalytic performance. In this work, we report the synthesis of gold nanoparticles functionalized with a series of thiol-decorated molecular silsesquioxanes, and their application as catalysts for the oxidative dehydrogenation of alcohols — a key transformation in organic synthesis and biomass valorization. Five thiolated silsesquioxanes were investigated featuring either three-dimensional (3D) core structures (ladder-type, double-decker, and cubic T₈-cage), or a two-dimensional (2D) scaffold based on the quasi-planar all-<em>cis</em> cyclotetrasiloxane (T₄) cyclic silanol. We show that the core topology and number of thiol groups affect nanoparticle size and aggregation, which in turn influence catalytic behavior. The tetrathiol-functionalized ladder-type and double-decker silsesquioxanes were the most efficient ligands, affording spherical Au nanoparticles with good yields, predominantly below 2 nm, and with a minor population around 5 nm. Double-decker-stabilized nanoparticles retained high catalytic activity and stability over five cycles in alcohol oxidative dehydrogenation, whereas ladder-type-stabilized NPs showed some sintering. Conversely, the octathiol-substituted cubic silsesquioxane caused significant nanoparticles aggregation, and the T₄-based ligand produced ultra-small Au nanoparticles with low yield and poor catalytic activity. These findings highlight the critical role of the silsesquioxane on nanoparticle stabilization and catalytic performance.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116342"},"PeriodicalIF":6.5,"publicationDate":"2025-07-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144748099","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":"Revealing the role of loaded aluminum in BiVO4-based solid solutions for photocatalytic overall water splitting","authors":"Huoshuai Huang ,&nbsp;Zhidong Wei ,&nbsp;Qianxiang Su ,&nbsp;Chen Wang ,&nbsp;Linlin Ma ,&nbsp;Mingxia Chen ,&nbsp;Zhi Jiang ,&nbsp;Yangzhou Sun ,&nbsp;Wenfeng Shangguan","doi":"10.1016/j.jcat.2025.116338","DOIUrl":"10.1016/j.jcat.2025.116338","url":null,"abstract":"<div><div>One-step excitation photocatalytic overall water splitting (OWS) is an important reaction for clean energy conversion, but the efficiency is limited by the severe bulk-phase photocarrier recombination. To address this challenge, aluminum loaded tetragonal zircon BiVO₄-based solid solution, Bi_0.5Y_0.5VO₄, materials (xat%Al-BYV) were successfully prepared in this study. Photocatalytic experiments showed that the optimized xat%Al-BYV exhibited a 11-fold enhancement in OWS performance compared to the pristine BYV. Structural characterizations confirmed that Al existed in the form of γ-Al₂O₃ and induced distortions of the VO₄ microstructure in the xat%Al-BYV via AlO₄, which enhanced the material polarization that facilitated the separation of bulk-phase photocarrier. Photoelectrochemical tests and transient absorption spectroscopy (TAS) confirmed the optimized carrier dynamics, and TAS further elucidated the mechanism by which interfacial γ-Al₂O₃ extracted photogenerated holes to inhibit photocarrier recombination. This work revealed the mechanism of Al loading to optimized BYV bulk-phase carrier dynamics via the synergistic effect of microstructure distortion-carrier extraction, and provided an insight for the design of other one-step excitation semiconductor materials in the future.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116338"},"PeriodicalIF":6.5,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737496","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":"Unraveling the steric effects of confined water within zeolite and their consequences on hydrogen isotope exchange","authors":"Hongbing Wang ,&nbsp;Xiaolin Zhou ,&nbsp;Jun Chen ,&nbsp;Dongping Wang ,&nbsp;Yunxi Yao ,&nbsp;Yifei Yang","doi":"10.1016/j.jcat.2025.116341","DOIUrl":"10.1016/j.jcat.2025.116341","url":null,"abstract":"<div><div>Confined water clusters within the microporous framework of zeolite positively or negatively influence the catalytic reaction rates and selectivities, because of their steric effects to the reactive intermediates and transition states differently. In this study, a series of supported Pt-zeolites (e.g. 1Pt/USY, 1Pt/MOR, 1Pt/Beta, 1Pt/ZSM-5 and 1Pt/ZSM-35) with the analogous Pt cluster size and the concentration of Brønsted acid sites (BAS) and the different pore structures were employed to investigate the catalytic roles of confined water clusters during H₂-HDO isotope exchange. The comparable reactive environments upon these bifunctional Pt catalysts enable them to share the identical reaction pathway during hydrogen isotope exchange. Specifically, water clusters are protonated on BAS to deliver deuteron and the subsequent hydrogen isotope exchange occurs at the interface of metal-water clusters by a synchronously bidirectional transfer, leading to the similar activation energy of 30.5 ± 4.0 kJ mol⁻¹. Nevertheless, the pore architectures of as-used zeolites affect the structure of confined water clusters in the form of one-dimensional oligomeric chains or three-dimensional bulk-like networks within the microporous frameworks, which constrains the hydrogen intrapore diffusion in the sub-nanometer scale and the subsequent reaction kinetic events to the different extents. As a result, the measured reaction rates upon these Pt-zeolite catalysts follow this order: 1Pt/USY&gt;1Pt/MOR&gt;1Pt/Beta&gt;1Pt/ZSM-5&gt;1Pt/ZSM-35. Collectively, this work shows that how the confined water within microporous environment affects the catalytic process, which also offers the mechanistic understanding of reaction chemistry in the restricted space.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116341"},"PeriodicalIF":6.5,"publicationDate":"2025-07-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144737498","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":"The new [As2Mo12CuII12(OH)12O50]6− anion cluster bundled by the [CuI(Pz)]+ chain with multiple reactional microenvironments for highly efficient synthesis of dimethyl carbonate","authors":"Yanli Yang ,&nbsp;Keke Guo ,&nbsp;Xue Bai ,&nbsp;Maochun Zhu ,&nbsp;Siyue Wang ,&nbsp;Ying Lu ,&nbsp;Shuxia Liu","doi":"10.1016/j.jcat.2025.116340","DOIUrl":"10.1016/j.jcat.2025.116340","url":null,"abstract":"<div><div>The direct synthesis of dimethyl carbonate (DMC) from CO₂ and methanol (MeOH) is a promising green method. However, its efficiency is still far from the practical application, due to the limited understanding of both the key structural factors affecting DMC synthesis and the rational design of efficient catalyst. Herein, we design and construct a porous supramolecular structure {[As₂Mo₁₂Cu^II₁₂(OH)₁₂O₅₀][Cu^I(pz)]₆}_n (As₂Mo₁₂Cu^II₁₂-[Cu^I-MOF]) with open active sites, which possesses abundant Lewis acid-base sites being conducive to strong adsorption of CO₂ and weak adsorption of MeOH, promoting the activation of CO₂ and MeOH as well as the rapid generation of key *CH₃OCOO intermediates. Furthermore, the structural characteristics of As₂Mo₁₂Cu^II₁₂-[Cu^I-MOF] enable them to form multiple reactional microenvironments, which greatly improve the utilization efficiency of CO₂ and MeOH, thereby achieving efficient synthesis of DMC. Finally, under the presence of a dehydrating agent, As₂Mo₁₂Cu^II₁₂-[Cu^I-MOF] exhibits excellent catalytic performance for DMC synthesis with the yield of 322.7 mmol g⁻¹. This work provides insights into the design of efficient catalysts for direct synthesis of DMC from CO₂ and MeOH.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116340"},"PeriodicalIF":6.5,"publicationDate":"2025-07-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144719803","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":"High selectivity and efficiency in 5-hydroxymethylfurfural oxidation: synergistic oxygen activation by Co-Nx sites on nitrogen-doped carbon supported single-atom cobalt","authors":"Shutian Lin ,&nbsp;Zijian Liu ,&nbsp;Yaocheng Xie ,&nbsp;Yuanhong Zhong ,&nbsp;Ming Sun ,&nbsp;Lin Yu","doi":"10.1016/j.jcat.2025.116337","DOIUrl":"10.1016/j.jcat.2025.116337","url":null,"abstract":"<div><div>2,5-Furandicarboxylic acid (FDCA), a pivotal polymer industry chemical, is primarily synthesized via the oxidation of 5-hydroxymethylfurfural (HMF). Non-precious metal catalysts exhibit significant potential in this process, yet harsh conditions and inefficient atom utilization hinder their broader use. Herein, a Co-based catalyst (Co_1.3-N-C) with highly dispersed Co single atoms, derived from zeolitic imidazolate frameworks (ZIFs), was successfully synthesized. It activates the adsorbed O₂ into both radicals and non-radicals with high catalytic efficacy through well-defined active sites (Co-N₄). The catalyst achieved a complete conversion of HMF to FDCA within one hour at 90 °C under 0.1 MPa O₂, with a yield of 99.6% and an impressive FDCA formation rate of 52.34 μmol min⁻¹ g⁻¹. This performance is comparable to the activity of many reported precious and non-precious metal catalysts. The catalytic mechanism, along with the roles of distinct reactive species, superoxide radical (O₂^<img>−) and singlet oxygen (¹O₂), at various stages of the selective oxidation of HMF to FDCA, was elucidated through theoretical calculations. The results highlight the excellent activity and high selectivity of Co_1.3-N-C, which is promising for the sustainable production of bio-based chemicals and materials.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116337"},"PeriodicalIF":6.5,"publicationDate":"2025-07-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144712442","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":"Modulating surface charge and offering hydrogen bonding for copper-based materials toward efficient electrocatalytic CO2 to ethylene","authors":"Zhen Liu ,&nbsp;Xiao-Yun Li ,&nbsp;Xiao-Yu Yang ,&nbsp;Zhan Liu ,&nbsp;Yu Li ,&nbsp;Yi-Yong Huang ,&nbsp;Zhao Deng ,&nbsp;Shen Yu ,&nbsp;Ming-Hui Sun ,&nbsp;Li-Hua Chen ,&nbsp;Bao-Lian Su ,&nbsp;Yi-Long Wang","doi":"10.1016/j.jcat.2025.116336","DOIUrl":"10.1016/j.jcat.2025.116336","url":null,"abstract":"<div><div>Cuprous oxide (Cu₂O) has been regarded as a highly promising category of electrocatalyst for carbon dioxide reduction reaction (CO₂RR). Nevertheless, the development of highly efficient Cu-based electrocatalysts for the CO₂-to-ethylene conversion as well as the elucidation of the possible catalytic mechanism, remain challenging areas of research. This is due to the fact that the electrocatalytic CO₂RR conversion to ethylene (C₂H₄) is a process comprising numerous steps and a sophisticated electrocatalytic mechanism. The absence of a comprehensive understanding of the reaction process is likely to impose significant limitations on the design of highly efficient Cu-based electrocatalysts. In this work, the nitrogen-doped Cu₂O nanocubes modified with dodecylamine have been synthesized <em>via</em> a facile refluxing strategy to efficiently promote the conversion of CO₂ to C₂H₄. The present work focuses on a comprehensive analysis of the underlying mechanisms that underpin the enhanced CO₂RR activity of the as-synthesized electrocatalysts. First, the introduction nitrogen atoms into electrocatalysts can efficiently modulate the charge of Cu sites, which favors the adsorption of the *CO intermediate. Additionally, the presence of hydrogen bonding serves to stabilize the *CHO intermediate and weaken the C<img>O bond of the O*CCHO intermediate, thereby facilitating the hydrogenation process to the O*CCHOH intermediate. Last but not least, our electrocatalyst present a significant advantage over both the dodecylamine-modified electrocatalyst and the electrocatalyst that has not undergone N doping and dodecylamine in the dehydroxylation of OH*CHCH₂ to *CHCH₂ intermediates. This is due to the configuration transformation of the *CHCH₂ intermediate, which favors the formation of C₂H₄. Our work proposes a feasible strategy for modulating charge coupled to offering hydrogen bonding for the design and synthesis of the Cu-based electrocatalysts, with the objective of achieving efficient conversion of CO₂ to C₂H₄.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116336"},"PeriodicalIF":6.5,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701834","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":"Acid-base pairs of acidic ionic liquids-functionalized covalent triazine frameworks with controllable morphology for boosting C–O bond cleavage of carbohydrate","authors":"Xiaofei Liu,&nbsp;Daiyu Song,&nbsp;Yunyun Liu,&nbsp;Zhao Huang,&nbsp;Xinyao Wang,&nbsp;Kezhi Wang,&nbsp;Yuxin Yang,&nbsp;Yihang Guo","doi":"10.1016/j.jcat.2025.116335","DOIUrl":"10.1016/j.jcat.2025.116335","url":null,"abstract":"<div><div>The cleavage of C–O bonds in biomass-derived carbohydrates is of great significance for the conversion of biomass to chemicals and fuels. We demonstrated that various F127-directed covalent triazine frameworks functionalized by sulfonic acid-based ionic liquids ([C₃N][OTf]-FCTF) were synthesized by a two-step synthesis process. The interesting morphology of spherical nanofiber of the [C₃N][OTf]-FCTF(0.25)-10 catalyst was obtained by carefully adjusting the usage of both F127 and ethanol in the synthetic system. The 5-hydroxymethylfurfural synthesis reaction parameters of were first optimized using the [C₃N][OTf]-FCTF(0.25)-10 <em>via</em> response surface methodology. The [C₃N][OTf]-FCTF(0.25)-10 exhibited high catalytic activity, and outperformed other CTF-based catalysts with different morphologies and commercial solid acids in the conversion of carbohydrates (e.g., fructose, inulin, sucrose and honey). This is due to the advantages of the loose spherical nanofiber, the rich N-containing units, the suitable Brønsted acid nature and the adjacent acid-base pairs on the surface of the catalyst. The high Brønsted acidity of [C₃N][OTf]-FCTF(0.25)-10 played a positive role in the selective synthesis of levulinic acid from carbohydrates. The theoretical calculations demonstrated that discrepancies in electron cloud distribution between constructed acid-base pairs and N-rich groups in the catalyst could facilitate the cleavage of C–O bonds in fructose molecules. The Fukui function combined with experimental results elucidated the reaction pathways. The robust interaction between –[C₃N][OTf] groups and frameworks ensured the excellent reusability of [C₃N][OTf]-FCTF catalysts. This study will provide a novel approach for synthesizing CTF-based solid acids with controllable morphology, enabling the high-value utilization of carbohydrates.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116335"},"PeriodicalIF":6.5,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144710829","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":"Caffeine carbon supported reusable cobalt catalyzed reductive amino formylation of carbonyl compound using ammonium formate","authors":"Sadhan Dey ,&nbsp;Seema D. Thakur ,&nbsp;Trishit Roy ,&nbsp;Anirban Sau ,&nbsp;Ratan Debnath ,&nbsp;Rajaram Bal ,&nbsp;Sabuj Kundu","doi":"10.1016/j.jcat.2025.116334","DOIUrl":"10.1016/j.jcat.2025.116334","url":null,"abstract":"<div><div>Reductive amino formylation (RAF) of carbonyl compounds employing ammonium formate faces major obstacles due to selectivity issues. Utilizing biowaste-derived caffeine carbon, the development of sustainable catalytic systems for diverse organic transformations is an exciting area of research. In this outlook, we have established a caffeine carbon-supported reusable cobalt-based catalytic system for the selective synthesis of <em>N</em>-formylated products via RAF of a variety of carbonyl compounds using ammonium formate as an N1, C1, and hydrogen source. Herein, we have developed an efficient catalytic system by fine-tuning the Co-Nx and nitrogen content for effective utilization of ammonium formate towards RAF of carbonyl compounds. The practical application of this methodology was demonstrated through gram-scale synthesis and RAF of acetophenone derivatives containing biologically relevant motifs. Various kinetic and control experiments were performed to understand the catalytic process. The catalyst was recycled up to the 7^th time without significant loss of catalytic activity.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116334"},"PeriodicalIF":6.5,"publicationDate":"2025-07-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144701835","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":"Indium-powered boost: Enhancing the photocatalytic efficiency of π-expanded pyrazinoporphyrins in sulfide oxidation","authors":"Ekaterina S. Shremzer ,&nbsp;Daria A. Polivanovskaia ,&nbsp;Kirill P. Birin ,&nbsp;Aslan Yu. Tsivadze","doi":"10.1016/j.jcat.2025.116327","DOIUrl":"10.1016/j.jcat.2025.116327","url":null,"abstract":"<div><div>A crucial enhancement of photocatalytic performance of a series of novel π-expanded indium(III) porphyrins bearing annelated pyrazine heterocycle substituted by or fused with various peripheral fragments, namely ethyl, 4-methylphenyl, phenanthrene, phenanthroline, and acenaphthene, has been revealed and investigated in detail. The introduction of In(III) ion into the porphyrin cavity resulted in significant increase in both the photostability and photocatalytic activity of the porphyrin-based photosensitizers. The synthesized In(III) pyrazinoporphyrins demonstrated exceptional conversion rates across a representative set of substrates in selective photocatalytic oxidation of organic sulfides to the corresponding sulfoxides. The study also underscored the crucial role of solvent selection in optimization of photocatalytic oxidation of sulfides. Notably, the phenanthrene-appended In(III) pyrazinoporphyrinate exhibited outstanding photocatalytic efficiency even at extremely low loading, achieving an exceptionally high TOF of 309 000 h⁻¹ in oxidation of dibutyl sulfide. Furthermore, gram-scale photooxidation of sulfides showed remarkable catalytic efficiency and scalability under mild conditions in the presence of «green» solvents.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"450 ","pages":"Article 116327"},"PeriodicalIF":6.5,"publicationDate":"2025-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144684941","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}