ACS Catalysis 最新文献

{"title":"Cobalt-Catalyzed Enantioselective Synthesis of S-Stereogenic Sulfinamides Enabled by P-Stereogenic Phosphines with Aryl and Alkenyl Boronic Acids","authors":"Yu Wang, Zhihan Zhang, Qinglei Chong, Fanke Meng","doi":"10.1021/acscatal.5c04608","DOIUrl":"https://doi.org/10.1021/acscatal.5c04608","url":null,"abstract":"Sulfur-stereogenic sulfinamides are not only key structures for biologically active molecules, ligands, and organocatalysts but also versatile intermediates to access a variety of organosulfur compounds containing S(IV) or S(VI) stereogenic centers. Despite progress in this field, catalytic enantioselective construction of sulfur-stereogenic centers remains a significant challenge. Herein, we present a cobalt-catalyzed protocol for catalytic enantioselective aryl and alkenyl addition to sulfinylamines with aryl and alkenyl boronic acids, affording a broad scope of sulfur-stereogenic sulfinamides with high efficiency and enantioselectivity. A phosphorus-stereogenic phosphinooxazoline ligand was developed, enabling the introduction of alkenyl groups onto the sulfur-stereogenic centers. Functionalization provided a variety of sulfur-stereogenic S(IV) and S(VI) compounds. Mechanistic studies and DFT calculations have been conducted to elucidate the reaction mechanism and the origin of enantioselectivity.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911312","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":"QM/MM Insights into Mechanism-Based Inactivation of Human CYP3A4: Formation of a Nitrosoalkane Intermediate from Erythromycin","authors":"Dongxiao Yue, Hajime Hirao","doi":"10.1021/acscatal.5c03511","DOIUrl":"https://doi.org/10.1021/acscatal.5c03511","url":null,"abstract":"Erythromycin, a naturally occurring 14-membered macrolide antibiotic, is widely used to treat various bacterial infections. CYP3A4 is the primary enzyme responsible for erythromycin metabolism in humans. However, this metabolic process can lead to the formation of a nitrosoalkane intermediate, ultimately resulting in mechanism-based inactivation (MBI) of the enzyme. Despite its clinical significance, the precise mechanistic pathway underlying the formation of this intermediate remains largely unclear. In this study, we employed molecular docking and molecular dynamics (MD) simulations to identify the most plausible catalytically competent binding mode of erythromycin in CYP3A4, which differs markedly from that observed in the available crystal structure. Based on the predicted binding mode, we carried out hybrid quantum mechanics/molecular mechanics (QM/MM) calculations, which suggest that erythromycin undergoes N-demethylation at its tertiary amine as the initial metabolic step, yielding a secondary amine. Rather than undergoing further N-dealkylation, this intermediate is N-hydroxylated to form an N-hydroxy secondary amine. This species is subsequently dehydrogenated to produce a nitrone intermediate, which undergoes methylene cleavage to generate a nitrosoalkane that coordinates to the ferrous heme iron, thereby contributing to CYP3A4 inactivation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911326","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":"Remote Biocatalytic Stereoselective Synthesis of Axially and Centrally Chiral Alkylidene Cyclopentanols","authors":"Xiao-Jian Zhou, Jin-Tao Gao, Lu Feng, Kuan Qian, Ming-Qiang Zhou, Yong-Zheng Chen","doi":"10.1021/acscatal.5c03835","DOIUrl":"https://doi.org/10.1021/acscatal.5c03835","url":null,"abstract":"Axially chiral alkylidene cycloalkanes are important scaffolds found in various bioactive molecules, yet their synthetic methods remain underdeveloped. In particular, the construction of alkylidene cycloalkanes bearing both axial and central chiralities poses a significant challenge. In this work, we present an efficient and green strategy for synthesizing axially chiral alkylidene cyclopentanones and cyclopentanols through a remotely controlled kinetic resolution (KR) approach. Directed evolution of an alcohol dehydrogenase (TbSADH) from Thermoethanolicus brockii yielded a variant (TbSADH-I86A/W110R/Y267L) capable of catalyzing the stereoselective reduction, affording a diverse range of axially and centrally chiral alkylidene cyclopentanols with high enantio- and diastereoselectivity, as well as excellent selectivity factors (ee up to 99%, dr up to >99:1, and s up to >100). Additionally, we demonstrated the stereodivergent synthesis of alcohols featuring both axial and central chirality via chemoenzymatic methods. To elucidate the molecular recognition mechanisms, molecular docking studies were conducted, revealing that the altered active pocket geometry of the mutant enzyme enhances both activity and enantioselectivity. This methodology not only provides a novel biocatalytic platform for accessing nonatropisomeric axially chiral structures with dual chirality elements but also underscores the potential of enzymatic strategies as powerful tools for remote stereocontrol in synthetic organic chemistry.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"22 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911316","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":"1,4-Arylalkylation of Butadiene with Aryl Bromides and Amino Acids Enabled by Photo-Induced Chiral Aldehyde/Palladium Catalysis","authors":"Jian-Hua Liu,&nbsp;Lei Xu,&nbsp;Wei Wen,&nbsp;Zhu-Lian Wu,&nbsp;Tian Cai,&nbsp;Yan-Min Huang*,&nbsp;Yu Lan* and Qi-Xiang Guo*,&nbsp;","doi":"10.1021/acscatal.5c02967","DOIUrl":"10.1021/acscatal.5c02967","url":null,"abstract":"<p >Butadiene is one of the most important chemical feedstocks used for the construction of value-added molecules. However, much of the existing endeavors have primarily focused on the achiral synthesis. Alternatively, although the aryl radical-involved transformations have been extensively disclosed, the corresponding catalytic asymmetric methodologies remain exceedingly rare. In this study, we present a highly efficient three-component asymmetric 1,4-arylalkylation of butadiene utilizing readily available aryl bromides and NH₂-unprotected amino acid esters. This process is facilitated by photoinduced chiral aldehyde/palladium combined catalysis. A diverse array of chiral nonproteinogenic α,α-disubstituted α-amino acid esters with unique structures is generated with 35–81% yields and 71–98% ee values. The resulting products can be easily converted to other structurally diverse α-amino acids. Density functional theory (DFT) calculations indicate that the final enantioselectivity is governed by a synergistic reaction model that encompasses noncovalent interactions between Pd···Br···Zn as well as strong C–H···Br and π···π dispersion interactions.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 17","pages":"15734–15744"},"PeriodicalIF":13.1,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906647","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":"Electronic Configurations Effect of Ceria Nanowire-Based Catalysts for Efficient CO Oxidation","authors":"Tian Liu,&nbsp;Zhi-Yu Xian,&nbsp;Xiao-Fang Yu,&nbsp;Yan-Qiu Fu,&nbsp;Si-Zhe Sheng,&nbsp;Zhen He and Jian-Wei Liu*,&nbsp;","doi":"10.1021/acscatal.5c01128","DOIUrl":"10.1021/acscatal.5c01128","url":null,"abstract":"<p >Introducing transition metal elements is a powerful strategy to tailor the electrochemical properties of ceria nanostructures. However, the electronic configuration effect is still ambiguous. Herein, a series of ultrathin nanowire-based catalysts, Ce_1–<i>x</i>M_<i>x</i>O₂ (M = Cu, Fe, Co, and Ni), have been precisely synthesized, showing the lowered complete reaction temperatures (T₁₀₀) and enhanced catalytic efficiencies for efficient CO oxidation. Theoretical calculations elucidate that transition metals facilitate the catalytic process by weakening metal–oxygen bonds during CO adsorption and strengthening them during CO₂ desorption. The higher the saturation extent of 3<i>d</i> electrons, the stronger the promotion effect of the transition elements on CO oxidation. Therefore, the present work reveals the significance of the electronic configuration effect on transition metal-doped ceria nanomaterials, which contributes to developing superior catalysts for highly efficient CO oxidation.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 17","pages":"15745–15753"},"PeriodicalIF":13.1,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906649","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":"CaTS: Toward Scalable and Efficient Transition State Screening for Catalyst Discovery","authors":"Jun Yin, Wentao Li, Honghao Chen, Jiangjie Qiu, Huasheng Feng, Xiangya Xu, Qiuyan Jin, Xiaonan Wang","doi":"10.1021/acscatal.5c03945","DOIUrl":"https://doi.org/10.1021/acscatal.5c03945","url":null,"abstract":"Large-scale screening of materials via machine learning is emerging as an effective strategy for accelerating scientific discovery and industrial applications. Machine learning methods for transition state (TS)-based screening for catalysts remain underexplored due to the scarcity of TS data sets and the inherent challenges of TS searching tasks. Here, we present a framework for large-scale transition states screening for catalysts (CaTS), which uniquely bridges microscopic reaction kinetics and macroscopic computational efficiency by leveraging TS energy, a mechanistically rigorous yet computationally prohibitive descriptor. CaTS integrates automated structure generation with a machine learning force field-based nudged elastic band (NEB) method, enabling high-throughput TS exploration at 10⁴ the speed of density functional theory (DFT). Initially optimized and validated on a small-molecule TS database comprising 10,000 reactions (achieving sub-0.2 eV errors in TS energy prediction) and further applied to a metal–organic complex catalyst (0.16 eV MAE with only 327 training samples), CaTS achieves DFT-level accuracy at 0.01% computational cost. Scaling to over 1000 unseen metal–organic complex structures, it identifies top candidates validated by rigorous DFT. AI-assisted analysis using ChatGPT o3 and SHAP confirms that the predictions are consistent with mechanistic heuristics, providing theoretical validation for large-scale prediction. This paradigm shift from static descriptors to kinetic-resolution screening enables industrial-scale catalyst discovery with atomistic precision.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"17 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906645","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":"Impact of Acid Sites in ZSM-5 Zeolites on the Selective Catalytic Oxi-Upcycling of High-Density Polyethylene to Dicarboxylic Acid under Mild Conditions","authors":"Fan Yuan, Xueyang Hou, Kaili Wang, Yi Zhu, Guoli Chen, Yi Hao, Jingxiu Yang, Jingfeng Han, Rongrong Jia, Pimjai Pimbaotham, Yuwanda Injongkol, Siriporn Jungsuttiwong, Liyi Shi, Ping Cheng, Lei Huang","doi":"10.1021/acscatal.4c04987","DOIUrl":"https://doi.org/10.1021/acscatal.4c04987","url":null,"abstract":"The catalytic oxidation strategy has shown great potential in the upcycling of polyethylene (PE) into valuable chemicals that contain oxygenated groups. The development of inexpensive and efficient catalysts is highly required but remains challenging. Herein, we report that ZSM-5 zeolites could be used as an effective catalyst for the selective catalytic oxi-upcycling of high-density polyethylene (HDPE) into dicarboxylic acids within the C₄–C₁₇ range at 160 °C and 1.5 MPa air pressure with a reaction duration of 16 h. Among the three tested ZSM-5 zeolites (Si/Al = 38, 70, and 170), the sample with a Si/Al ratio of 38 exhibited the highest acid site density and, consequently, the best catalytic activity. Based on the model molecular reactions, detected intermediate species, and theoretical calculation, we propose that Bro̷nsted acid sites synergize with oxygen to drive the oxidation of PE via a carbenium ion (C⁺) mediated mechanism, which is beyond the conventional pathway of direct oxidation of PE molecular chains by a free radical mechanism. Besides, the ZSM-5 zeolite has the potential to be applied broadly in the oxi-upcycling of different PE feedstocks and PE plastic wastes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"22 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144911331","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":"Reconstruction-Dependent Coordination Descriptor for Selectivity toward C2+ Products of CO2 Electroreduction over Cu Catalysts","authors":"Xuning Wang, Haoxiang Xu, Daojian Cheng","doi":"10.1021/acscatal.5c03702","DOIUrl":"https://doi.org/10.1021/acscatal.5c03702","url":null,"abstract":"The electroreduction of CO₂ (CO₂ER) to multicarbon chemicals (C₂₊) catalyzed by copper (Cu) is a pivotal initiative for achieving carbon neutrality and green chemical production. However, a lack of quantitative structure-selectivity relationship hampers further advancement of Cu catalysts. Moreover, the inherent structural fluidity of Cu catalysts, which facilitates its surface reconstruction during the CO₂ER reaction, complicates the mutual verification and self-consistency between theoretical and experimental results. In this study, we employ grand-canonical first-principles calculations under solvent and cation effects to elucidate the negative correlation between C₂₊ selectivity in CO₂ER and the coordination saturation of monometallic Cu catalysts. Through systematic analysis of CO-induced reconstruction of various Cu surfaces, we introduce the concept of degree of reconstruction (DOR) to quantitatively characterize the dynamic behavior of Cu surfaces. Additionally, we propose reconstruction-dependent generalized coordination numbers (RD-GCNs) as a descriptor to accurately capture the C₂₊ selectivity trends observed in electrocatalytic environments. The identified negative correlation between RD-GCNs and C₂₊ selectivity demonstrates that a lower RD-GCN notably enhances C₂₊ selectivity, accurately reproducing the relative order of experimental Faradaic efficiency (FE) for C₂₊ products among Cu single-crystal slabs and rationalizing the C₂₊ selectivity trend among monometallic Cu nanostructures with diverse morphology and roughness from available experimental references. This work provides significant insights into the impact of dynamic structural fluxionality of Cu catalysts on C₂₊ product selectivity, which lays the theoretical foundation and broadens the ideas for rational design of Cu-based catalysts for electroreduction conversions of CO₂ to C₂₊ products.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"23 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-08-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144906646","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 Visible-Light-Induced ATRA Reactions Powered by the Symbiotic Relationship between Cu(II)/Cu(I) Phenanthroline Complexes","authors":"Sarah Arteta,&nbsp;Mawuli Deegbey,&nbsp;Nicolas Durand,&nbsp;Russell Kibbe,&nbsp;Johannes Floß,&nbsp;Alexandra T. Barth,&nbsp;David C. Muddiman,&nbsp;Elena Jakubikova,&nbsp;Oliver Reiser and Felix N. Castellano*,&nbsp;","doi":"10.1021/acscatal.5c03135","DOIUrl":"10.1021/acscatal.5c03135","url":null,"abstract":"<p >As photoredox catalysis continues to yield promising chemical transformations, there is an increased need to understand how specific photocatalysts function to improve reaction efficiencies while expanding their scope. Copper-phenanthroline-based photocatalysts such as <b>Cu</b>^<b>II</b><b>(dap)Cl</b>_<b>2</b> (dap = 2,9-di(<i>p</i>-anisyl)-1,10-phenanthroline) and <b>[Cu</b>^<b>I</b><b>(dap)</b>_<b>2</b><b>]Cl</b> were both found to be equally capable of olefin activation through electrophilic atom transfer radical addition (ATRA) reactions. Although these molecular catalysts have proven successful, many intermediates suggested in the proposed catalytic cycles have never been detected. One undetermined aspect in this chemistry is related to how one equivalent of <b>Cu</b>^<b>II</b><b>(dap)Cl</b>_<b>2</b> generates half of an equivalent of <b>[Cu</b>^<b>I</b><b>(dap)</b>_<b>2</b><b>]</b>^<b>+</b> during the photocatalytic sequence. To this end, we initially used more synthetically accessible model systems, namely, <b>[Cu</b>^<b>I</b><b>(dpp)</b>_<b>2</b><b>]Cl</b> and <b>Cu</b>^<b>II</b><b>(dpp)Cl</b>_<b>2</b> (dpp = 2,9-diphenyl-1,10-phenanthroline), to glean detailed mechanistic insights into this unusual symbiotic relationship. We directly detected several intermediates involved in the ATRA photocatalytic cycle using these model chromophores in conjunction with electronic spectroscopy, infrared matrix-assisted laser desorption electrospray ionization (IR-MALDESI) mass spectrometry, electronic structure calculations, EPR spin-trap experiments, and ¹H NMR spectroscopy. We found that the unique ligand lability and coordinating properties of acetonitrile enable both the in situ oxidation of <b>[Cu</b>^<b>I</b><b>(dpp)</b>_<b>2</b><b>]</b>^<b>+</b> by tosyl chloride into <b>Cu</b>^<b>II</b><b>(dpp)Cl</b>_<b>2</b> and the visible-light-induced homolysis of the Cu^II–Cl bond, which initiates the conversion to the Cu^I species <b>[Cu</b>^<b>I</b><b>(dpp)</b>_<b>2</b><b>][Cu</b>^<b>I</b><b>Cl</b>_<b>2</b><b>]</b>. The combined findings from the present study of the catalytic cycle demonstrate that the symbiotic relationship between <b>Cu</b>^<b>II</b><b>(dpp)Cl</b>_<b>2</b> and <b>[Cu</b>^<b>I</b><b>(dpp)</b>_<b>2</b><b>]</b>^<b>+</b>, as well as between <b>Cu</b>^<b>II</b><b>(dap)Cl</b>_<b>2</b> and <b>[Cu</b>^<b>I</b><b>(dap)</b>_<b>2</b><b>]</b>^<b>+</b>, is the critical factor enabling the ATRA photoreaction by departing from either photocatalyst.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 17","pages":"15657–15669"},"PeriodicalIF":13.1,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901484","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":"CuFeO2 Integrated with Orderly Stacked Multilamellar ZSM-5 Nanosheets for Highly Active and Selective Synthesis of Aromatics from CO2 Hydrogenation","authors":"Yang Cheng,&nbsp;Shujing Li,&nbsp;Han Li,&nbsp;Di Meng,&nbsp;Shuxian Zhang,&nbsp;Ming Qing,&nbsp;Min Pan,&nbsp;Fuyun Yang,&nbsp;Chengwei Wang,&nbsp;Lei Li,&nbsp;Guangbo Liu,&nbsp;Peng Qin,&nbsp;Chufeng Liu,&nbsp;Hanyao Song,&nbsp;Haozhe Feng,&nbsp;Hao Chen,&nbsp;Jifan Li*,&nbsp;Chun-Ling Liu,&nbsp;Noritatsu Tsubaki* and Wen-Sheng Dong*,&nbsp;","doi":"10.1021/acscatal.5c05268","DOIUrl":"10.1021/acscatal.5c05268","url":null,"abstract":"<p >Direct conversion of CO₂ to value-added aromatics using renewable hydrogen is gaining significant attention. However, achieving a high aromatic selectivity at high CO₂ conversion remains challenging. Herein, we report a high-performance bifunctional catalyst for CO₂ hydrogenation to aromatics, integrating CuFeO₂ with orderly stacked multilamellar ZSM-5 nanosheets (ML-ZSM-5), synthesized via a facile and low-cost hydrothermal route. This catalyst achieves a high aromatic selectivity of 68.4 and 31.4% light aromatics (BTX: benzene, toluene, and xylene) selectivity at high CO₂ conversion of 59.9%, while minimizing CH₄ and CO selectivity to 2.8 and 5.4%, respectively. In situ XRD and DRIFTS analyses reveal that CuFeO₂ exhibits a high carburization rate, generating abundant iron carbides and active surface CH<i>x</i> species, leading to the production of abundant long-chain olefin intermediates. The ML-ZSM-5 component, with its orderly multilayered nanosheet structure, exhibits great mass transfer and limited external surface acidity. This facilitates rapid diffusion of both olefin intermediates and aromatics, favorably shifting the equilibrium of CO₂ hydrogenation and subsequent aromatization, thereby enhancing CO₂ conversion and aromatics selectivity. Meanwhile, the efficient diffusion of hydrogen species away from ML-ZSM-5, coupled with their consumption by CuFeO₂ in the CO₂-FTS reactions, further enhances hydrogenation activity. Hence, a synergistic, “dual-gear conveyor belt” mechanism between the bifunctional components facilitates highly active and selective hydrogenation of CO₂ to aromatics. Furthermore, the limited external surface acidity of ML-ZSM-5 also improves the selectivity of BTX. This work offers a promising route to high-performance bifunctional catalysts for the selective hydrogenation of CO₂ to aromatics.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"15 17","pages":"15706–15721"},"PeriodicalIF":13.1,"publicationDate":"2025-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144901480","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}