Journal of Catalysis最新文献_第2页

Hydroxyl-facilitated efficient propane dehydrogenation over bare Ga2O3 via altering reaction pathway 通过改变反应路径，羟基促进裸Ga2O3上丙烷的高效脱氢

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.jcat.2026.116743

Salman Khan , Enxi Wu , Yi Dai , Kaijie Wang , Lixia Bao , Zhen Wang , Tong Wang , Qi Liu , Yaoyuan Zhang , Qin Wu , Daxin Shi , Kangcheng Chen , Guiyuan Jiang , Hansheng Li

{"title":"Hydroxyl-facilitated efficient propane dehydrogenation over bare Ga2O3 via altering reaction pathway","authors":"Salman Khan , Enxi Wu , Yi Dai , Kaijie Wang , Lixia Bao , Zhen Wang , Tong Wang , Qi Liu , Yaoyuan Zhang , Qin Wu , Daxin Shi , Kangcheng Chen , Guiyuan Jiang , Hansheng Li","doi":"10.1016/j.jcat.2026.116743","DOIUrl":"10.1016/j.jcat.2026.116743","url":null,"abstract":"<div><div>Designing suitable catalysts for catalytic processes involving alkanes and efficiently activating C−H bond in light alkanes are both theoretically and practically significant. The present study shows that bare Ga<sub>2</sub>O<sub>3</sub> without any supported species or dopants can effectively catalyze the PDH reaction. A clear structure–activity relationship based on crystallite size, acid density, and hydroxyl group density is established, the smaller the crystallite size, the higher the activity. Ga<sub>2</sub>O<sub>3</sub> with a smaller crystallite size owns a higher concentration of hydroxyl species and oxygen vacancies. Comprehensive experimental investigations and DFT calculations indicate that the presence of oxygen vacancy in Ga<sub>2</sub>O<sub>3</sub> decreases the apparent activation energy of PDH compared with the pristine Ga<sub>2</sub>O<sub>3</sub> surface. Importantly, the existence of hydroxyl groups on the Ga<sub>2</sub>O<sub>3</sub> surface can significantly improve the ability to activate C−H bond by altering the PDH reaction from a non-oxidative to the oxidative pathway at the initial stage. It is expected that these findings offer fundamental insights into regulating the physicochemical properties of metal oxides for efficient C−H bond activation and hydrogenation reactions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116743"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110690","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}

引用次数: 0

Engineering electronic structure to modulate active site environment for enhanced photocatalytic nitrogen fixation 调节活性位点环境以增强光催化固氮的工程电子结构

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.jcat.2026.116725

Xin Huang , Jingyu Ren , Razium Ali Soomro , Shoujian Fu , Zixuan Li , Mengxi Fu , Li Guo , Chunming Yang , Danjun Wang

{"title":"Engineering electronic structure to modulate active site environment for enhanced photocatalytic nitrogen fixation","authors":"Xin Huang , Jingyu Ren , Razium Ali Soomro , Shoujian Fu , Zixuan Li , Mengxi Fu , Li Guo , Chunming Yang , Danjun Wang","doi":"10.1016/j.jcat.2026.116725","DOIUrl":"10.1016/j.jcat.2026.116725","url":null,"abstract":"<div><div>Exploring advanced photocatalysts for efficient photocatalytic nitrogen reduction reaction (pNRR) by regulating their active site chemical environment to facilitate nitrogen molecule (N<sub>2</sub>) activation is very promising. Nevertheless, elucidating the effect of electronic structures refining on modulate the local chemical environment to promote N<sub>2</sub> activation remains challenging. Herein, a series of 3d transition metal cations (Mn, Fe, Co, Ni, Cu, Zn) were introduced into crystal lattice of Bi<sub>2</sub>WO<sub>6</sub> to precisely tailor its electronic structure and surface physical properties (surface energy, polarity force and London force). Based on aerobic photocatalytic pNRR performance and physical properties, Cu-doped Bi<sub>2</sub>WO<sub>6</sub> (Cu-BWO) was identified as the most promising candidate. Excited-state calculations indicate that Cu doping attenuates the Coulomb interaction between electrons and holes in Bi<sub>2</sub>WO<sub>6</sub>, triggering the exciton effect that enhance the separation efficiency of photogenerated carriers. Furthermore, the doped Cu<sup>2+</sup> ions act as the active site: the lowest unoccupied molecular orbital (LUMO, <span><math><mrow><msub><mtext>d</mtext><msup><mrow><mtext>z</mtext></mrow><mtext>2</mtext></msup></msub><mspace></mspace><mi>o</mi><mi>r</mi><mi>b</mi><mi>i</mi><mi>t</mi><mi>a</mi><mi>l</mi></mrow></math></span>) of Cu<sup>2+</sup> facilitates N<sub>2</sub> adsorption, while electrons in its highest occupied molecular orbital (HOMO, d<sub>xz</sub> orbital) interact with the antibonding orbital (LUMO, 1π<sub>g</sub>) of N<sub>2</sub>, thereby boosting the aerobic pNRR process. This work reveals, for the first time, that Cu doping refines local chemical environment of Bi<sub>2</sub>WO<sub>6</sub> through the electronic structure regulation, thus regulating its achieving efficient enhance aerobic pNRR.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116725"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111029","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}

引用次数: 0

Tailoring Au-Cu binary sites for CH4 partial oxidation to CH3OH and C2H5OH 为CH4部分氧化生成CH3OH和C2H5OH裁剪Au-Cu二元位

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-02-06 DOI: 10.1016/j.jcat.2026.116745

Jingting Jin , Wenzhi Li , LuLu Zhang , Xiaoyi Liu , Liqun Wang

{"title":"Tailoring Au-Cu binary sites for CH4 partial oxidation to CH3OH and C2H5OH","authors":"Jingting Jin , Wenzhi Li , LuLu Zhang , Xiaoyi Liu , Liqun Wang","doi":"10.1016/j.jcat.2026.116745","DOIUrl":"10.1016/j.jcat.2026.116745","url":null,"abstract":"<div><div>Using monometallic copper (Cu) catalysts to selectively oxidize methane into clean fuels such as alcohols holds profound practical importance. However, Cu species remain constrained by insufficient methane activation at low temperature and over-oxidation with elevated temperature. This work proposed a strategy employing chemical reduction to enhance the homogeneity of active species, eliminating the harmful copper oxide species (CuO<sub>x</sub>) while enabling the construction of Au-O-Cu sites, and achieved a high alcohol productivity (64.40 and 65.73 μmol/g<sub>cat</sub>/h for methanol and ethanol, respectively) and selectivity (83.75%) under continuous flow at 250 °C. It is evidenced that the incorporation of gold (Au) promoted the polarization of adjacent Cu atoms’ d-orbitals, strengthening their coupling with methane and molecular oxygen. This electronic modulation concurrently downshifts Cu’s d-band center, weakening the adsorption strength of key intermediates, thus boosting the selectivity. Additionally, a catalytic domain with high electron localization emerged around the Au atom, providing additional anchoring sites for extra *CH<sub>4,</sub> which contributed to the co-formation of ethanol. These findings offered a viable strategy to circumvent the bottlenecks of conventional Cu-based catalysts, showcased the considerable potential of noble metal-transition metal synergy, and paved a solid pathway for designing advanced catalysts for methane conversion.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116745"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135419","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}

引用次数: 0

In-situ construction of durable Cu+ species for the catalytic hydrodeoxygenation of biomass-derived aldehydes 原位构建耐用Cu+物种用于催化生物质衍生醛的加氢脱氧

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-02-09 DOI: 10.1016/j.jcat.2026.116752

Yuting Luo, Qingyi Lv, Huai Liu, Rui Zhang, Wenlong Jia, Lincai Peng

{"title":"In-situ construction of durable Cu+ species for the catalytic hydrodeoxygenation of biomass-derived aldehydes","authors":"Yuting Luo, Qingyi Lv, Huai Liu, Rui Zhang, Wenlong Jia, Lincai Peng","doi":"10.1016/j.jcat.2026.116752","DOIUrl":"10.1016/j.jcat.2026.116752","url":null,"abstract":"<div><div>The structural reconstruction of Cu-based catalysts during the hydrodeoxygenation (HDO) process typically leads to the loss of active Cu<sup>+</sup> species and catalyst sintering, resulting in catalyst deactivation. Herein, we found that Pr-doped CuO<sub>x</sub> catalyst undergoes in-situ reconstruction to generate stable Cu<sup>+</sup> species during the HDO of vanillin (VAN) to 2-methoxy-4-methylphenol (MMP). This affords a high MMP yield of 85.5% using methanol as both the solvent and hydrogen donor, which is significant higher than that of pristine CuO<sub>x</sub> and previously reported catalysts for the HDO of VAN in MeOH. Electronic interactions between Pr dopants and the CuO<sub>x</sub> matrix strengthen the Cu–O bonds and stabilize Cu<sup>+</sup> species, thereby increasing the density of acidic sites and oxygen vacancies in the catalyst. This not only promotes MeOH decomposition for H<sub>2</sub> generation, but also facilitates VAN adsorption and activation, thereby boosting HDO activity. This work offers new insights for the in-situ construction of highly active and durable Cu<sup>+</sup> sites in Cu-based catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116752"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146679","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}

引用次数: 0

Substrate-activated Shvo catalyst for the solvent/promoter-free cyclization of diamines to piperidines and analogues 无溶剂/促进剂的二胺环化成哌啶和类似物的底物活化Shvo催化剂

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-01-31 DOI: 10.1016/j.jcat.2026.116720

Chuanmei Wang , Yihan Zhang , Ting Wang , Yanwei Cao , Zihang Yin , Houyu Tao , Zijun Huang , Dongyun Chen , Xianjie Fang , Jianmei Lu , Lin He

{"title":"Substrate-activated Shvo catalyst for the solvent/promoter-free cyclization of diamines to piperidines and analogues","authors":"Chuanmei Wang , Yihan Zhang , Ting Wang , Yanwei Cao , Zihang Yin , Houyu Tao , Zijun Huang , Dongyun Chen , Xianjie Fang , Jianmei Lu , Lin He","doi":"10.1016/j.jcat.2026.116720","DOIUrl":"10.1016/j.jcat.2026.116720","url":null,"abstract":"<div><div>Piperidine derivatives serve as crucial synthetic building blocks for pharmaceuticals and agrochemicals. With breakthroughs in the production capacity of diamines (such as 2-methylpentanediamine and 1,5-pentanediamine), employing cyclization strategies to access piperidine frameworks has garnered increasing attention. Herein, we report an efficient strategy to rapidly access piperidines via a “hydrogen-borrowing” mechanism over Shvo Ru catalysis without any additives. Firstly, the interaction between the Shvo Ru complex and diamines was investigated by <sup>1</sup>H NMR, FT-IR, mass spectrometry, and DFT calculations, revealing the role of diamines in dissociating the Shvo pre-catalyst and facilitating the formation of reactive intermediates. Based on this observation, Shvo-based catalysts with efficient activity for the solvent/promoter-free cyclization of diamines to piperidines were developed. This catalytic system is applicable not only to 100-gram scale-up synthesis with a record-high turnover number (TON) of 8645 and excellent selectivity (>99%), but also remains stable for over 4 cycles without significant loss of activity. Finally, the catalytic mechanism of the Shvo Ru-mediated, solvent/promoter-free cyclization of diamines to piperidines was proposed by DFT calculations and control experiments.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116720"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095947","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}

引用次数: 0

Metal nitrate in acetonitrile-driven aerobic oxidative cleavage of alkynes to carboxylic acids under mild conditions 金属硝酸盐在乙腈驱动的有氧氧化裂解条件下生成羧酸

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-01-27 DOI: 10.1016/j.jcat.2026.116719

Chao Xie , Zejun Liu , Huichao Wang , Qidong Hou , Hengli Qian , Zhiwei Jiang , Meiting Ju

{"title":"Metal nitrate in acetonitrile-driven aerobic oxidative cleavage of alkynes to carboxylic acids under mild conditions","authors":"Chao Xie , Zejun Liu , Huichao Wang , Qidong Hou , Hengli Qian , Zhiwei Jiang , Meiting Ju","doi":"10.1016/j.jcat.2026.116719","DOIUrl":"10.1016/j.jcat.2026.116719","url":null,"abstract":"<div><div>The cleavage of C<img>C bond in alkynes represents a promising strategy for the functional group transformation of alkyne compounds. However, balancing reactivity and selectivity remains a significant challenge due to its high bond dissociation energy and the inherently complex reaction pathways involved. In this work, we report a mild aerobic oxidative cleavage protocol for alkyne C<img>C bonds using commercially available nitrates as catalysts in acetonitrile, affording carboxylic acids in good to excellent yields. This approach exhibits broad functional group tolerance, being applicable to both unactivated alkynes and substrates bearing oxidation-sensitive groups. Mechanistic investigations <em>via</em> EPR, FT-IR, and NMR spectroscopy reveal that the excellent catalytic performance stems from the formation of coordination intermediates between the alkyne and metal nitrate. These intermediates are stabilized by acetonitrile through ion–dipole interactions—a stabilization effect that not only promotes alkyne activation and facilitates oxygen atom transfer (OAT) from nitrate to the C<img>C bond but also drives the reduction of nitrate to nitrogen oxides. These nitrogen oxides subsequently act as free-radical initiators to trigger a chain reaction, accelerating the oxidative cleavage of the C<img>C bond, with molecular oxygen serving as the terminal oxidant.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116719"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146056546","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}

引用次数: 0

Insight into the activation mechanism of methylene C–H bond over Ce–Al composite oxide Ce-Al复合氧化物上亚甲基C-H键活化机理的探讨

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-02-11 DOI: 10.1016/j.jcat.2026.116762

Xiangwei Ren , Yue Zhang , Shuzhen Lyu , Li Wang , Ruichen Liu , Guozhu Liu , Rongrong Zhang

{"title":"Insight into the activation mechanism of methylene C–H bond over Ce–Al composite oxide","authors":"Xiangwei Ren , Yue Zhang , Shuzhen Lyu , Li Wang , Ruichen Liu , Guozhu Liu , Rongrong Zhang","doi":"10.1016/j.jcat.2026.116762","DOIUrl":"10.1016/j.jcat.2026.116762","url":null,"abstract":"<div><div>Oxidation of methylene compounds remains a critical challenge due to the difficult activation of C–H bond. Herein, Ce–Al composite oxide was prepared and employed for oxidation of 2-alkyl-anthrone and anthracene to corresponding anthraquinone (AQ) which is used widely in the H<sub>2</sub>O<sub>2</sub> production by the anthraquinone process and fine chemical industries, with air at mild conditions. Characterization results show that incorporation of Ce, existing partially in CeAlO<sub>3</sub> phase, results in the generation of oxygen vacancies and enhancement of reducibility. The optimal Ce–Al composite oxide (10%CeAl) exhibits superior performance in oxidation of 2-alkyl-anthrone and anthracene to AQ. The conversion of 100% could be achieved for 2-alkyl-anthrone to AQ at reaction time of 8 h and for 2-alkyl-anthracene to AQ at 15 h over 10%CeAl, with 100% selectivity. <em>In-situ</em> electron paramagnetic resonance measurements and DFT calculations reveal that the Ce–O–Al structure in CeAlO<sub>3</sub> phase promotes the formation of carbon-centered radical R<sup>•</sup> through altering the C–H cleavage mechanism from hydrogen atom transfer to proton-coupled electron transfer (PCET), and superoxide anion radicals (O<sub>2</sub><sup>•−</sup>) formed on oxygen vacancies promote oxidation of R<sup>•</sup>.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116762"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146161097","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}

引用次数: 0

Oxygen-vacancy-enriched MoO3 quantum dots anchored on sulfur-vacancy-rich Zn3In2S6 heterostructures for boosted hydrogen peroxide photosynthesis from pure water 富氧空位MoO3量子点锚定在富硫空位Zn3In2S6异质结构上，促进纯水过氧化氢光合作用

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-02-03 DOI: 10.1016/j.jcat.2026.116724

Cheng-Jie Zheng , Ting Wang , Ren-Chang Zhang , Ke Xu , Zhi-Cai He , Jian Zhang , Guo-Bo Huang , Mingyuan Wang , Guiwu Liu , Wei Chen

{"title":"Oxygen-vacancy-enriched MoO3 quantum dots anchored on sulfur-vacancy-rich Zn3In2S6 heterostructures for boosted hydrogen peroxide photosynthesis from pure water","authors":"Cheng-Jie Zheng , Ting Wang , Ren-Chang Zhang , Ke Xu , Zhi-Cai He , Jian Zhang , Guo-Bo Huang , Mingyuan Wang , Guiwu Liu , Wei Chen","doi":"10.1016/j.jcat.2026.116724","DOIUrl":"10.1016/j.jcat.2026.116724","url":null,"abstract":"<div><div>The development of efficient photocatalytic systems for hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) production from pure water remains a huge challenge due to rapid charge recombination and insufficient redox capability in single-component photocatalysts. Herein, we successfully constructed the S-scheme oxygen-vacancy-enriched MoO<sub>3</sub> quantum dots (Ov-MoQDs)/sulfur-vacancy-rich Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub> (Sv-ZIS) heterostructures by coupling Sv-ZIS nanosheets with Ov-MoQDs. The optimized 3Ov-MoQDs/Sv-ZIS sample achieves an outstanding H<sub>2</sub>O<sub>2</sub> production rate of 85.8 ± 3.1 μM under visible light illumination for 1 h in the pure water, which is about 3.5 and 45.1 times higher than those of Sv-ZIS and Ov-MoQDs, respectively. Through comprehensive in situ and ex situ characterizations combined with theoretical calculations, we demonstrate that the enhanced activity stems from efficient charge separation and transfer across the heterogeneous interfaces via an S-scheme mechanism. Furthermore, the H<sub>2</sub>O<sub>2</sub> photosynthesis over Ov-MoQDs/Sv-ZIS heterostructures is found to proceed through a two-step single-electron oxygen reduction reaction (ORR) pathway. This work provides valuable insights into the rational design of advanced heterostructured photocatalysts for sustainable chemical synthesis.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116724"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110688","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}

引用次数: 0

Mechanistic Insights on the β-(Z) alkyne hydrosilylation by a NHC-based Cp*Rh(III) catalyst: from catalyst design to an alternative model for H-Si activation 基于nhc的Cp*Rh（III）催化剂对β-(Z)炔氢硅化反应的机理研究：从催化剂设计到H-Si活化的替代模型

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-01-31 DOI: 10.1016/j.jcat.2026.116721

Isabel Poves-Ruiz , Beatriz Sánchez-Page , M. Victoria Jiménez , Miguel Gallegos , Julen Munarriz , Vincenzo Passarelli , Jesús J. Pérez-Torrente

{"title":"Mechanistic Insights on the β-(Z) alkyne hydrosilylation by a NHC-based Cp*Rh(III) catalyst: from catalyst design to an alternative model for H-Si activation","authors":"Isabel Poves-Ruiz , Beatriz Sánchez-Page , M. Victoria Jiménez , Miguel Gallegos , Julen Munarriz , Vincenzo Passarelli , Jesús J. Pérez-Torrente","doi":"10.1016/j.jcat.2026.116721","DOIUrl":"10.1016/j.jcat.2026.116721","url":null,"abstract":"<div><div>In-depth studies on the residual hydrosilylation catalytic activity of samples of compound [Cp*RhI{(MeIm)<sub>2</sub>CH<sub>2</sub>}]<sup>+</sup>, bearing an unfunctionalized bis-NHC ligand, lead to the discovery of the excellent catalytic performance of the simple complex [Cp*RhI<sub>2</sub>(IMe)] (IMe = 1,3-dimethylimidozol-2-ylidene). This compound efficiently catalyzes the hydrosilylation of wide a range of terminal alkynes, with complete regio- and stereoselectivity toward the thermodynamically less stable β-(Z)-vinylsilane isomer. The reaction mechanism has been explored by DFT calculations. The reaction seems to proceed through an ionic outer-sphere mechanism, involving heterolytic activation of the hydrosilane assisted by the rhodium center and a solvent molecule (acetone). In the absence of acetone, a metal–ligand cooperation reaction pathway is proposed, in which the Cp* ligand acts as a proton-relay within the coordination sphere of the Rh(III) center. The cooperative activation of the hydrosilane by the metallocene moiety of the catalyst precursor generates a reactive Rh(I)–silyl intermediate bearing a pentamethylcyclopenta-1,3-diene ligand, [η<sup>4</sup>-Cp*H], formed through protonation of the Cp* moiety.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116721"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095953","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}

引用次数: 0

Influence of tailoring acidic sites and silicon distribution of SAPO-11 zeolite via in-situ Zn modification for superior hydroisomerization of Fischer-Tropsch wax 原位锌改性对SAPO-11沸石酸性位和硅分布对费托蜡加氢异构化的影响

IF 6.5 1区化学

Journal of Catalysis Pub Date : 2026-04-01 Epub Date: 2026-01-30 DOI: 10.1016/j.jcat.2026.116716

Fan Shao, Fengzhi Guo, Tianyu Bai, Rongrong Li, Shixuan Guo, Jinxiao Sun, Yasong Zhou, Wenbin Huang, Lu Gong, Gang Wang, Qiang Wei

{"title":"Influence of tailoring acidic sites and silicon distribution of SAPO-11 zeolite via in-situ Zn modification for superior hydroisomerization of Fischer-Tropsch wax","authors":"Fan Shao, Fengzhi Guo, Tianyu Bai, Rongrong Li, Shixuan Guo, Jinxiao Sun, Yasong Zhou, Wenbin Huang, Lu Gong, Gang Wang, Qiang Wei","doi":"10.1016/j.jcat.2026.116716","DOIUrl":"10.1016/j.jcat.2026.116716","url":null,"abstract":"<div><div>Improving the performance of hydroisomerization catalysts for jet fuel production remains a considerable challenge, due to the difficulty in precisely controlling the balance between metal and acid functions. Although zinc modification offers a promising strategy to enhance the synergy, the underlying mechanistic understanding of Zn-induced framework repair and reconstruction remains unclear, blocking the rational design of bifunctional catalysts. In this work, A series of Zn-modified SAPO-11 zeolites with tunable ZnO/Al<sub>2</sub>O<sub>3</sub> ratios were synthesized via <em>in-situ</em> doping technique. Characterization results revealed that Zn substitution for Al altered the silicon incorporation environment. The formation of Si-O-Zn bonds (NH<sub>3</sub> adsorption energy = -0.99 eV) indicated weaker acidity than Si-O-Al bonds (−1.44 eV). At ZnO/Al<sub>2</sub>O<sub>3</sub> = 0.5% doping, isolated P-O-Zn bonds promoted the dispersion and dissolution of large silicon islands (Si(4Si)), increasing weak Brønsted acid sites. At higher Zn doping, the mechanism shifted inducing Si redistribution and forming medium-strong Brønsted acid sites. Namely, a dual role of Zn was identified as framework repair at low loading and framework reconstruction at high loading. The weakened and dispersed acidity enhanced Pt dispersion and reducibility, enabling Pt/(0.75ZnSAPO-11 + ASA) catalyst to deliver the highest iso-C<sub>22</sub> yield (30.9%) and selectivity (58.7%), with double-branched isomer yield (10.8%) and selectivity (20.6%). This work highlights the underlying mechanism of Zn modification in catalyst framework, and demonstrates its implications for enhancing the industrial application of Zn-modified catalysts in Fischer-Tropsch wax upgrading and jet fuel cold-flow performance.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116716"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095946","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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