Pub Date : 2026-01-29DOI: 10.1021/acscatal.5c08219
Zhiwen Gan, Long Yu, Yixu Zhou, Yongzhen Liu, Jiyu Tong, Shi Chen, Yuxiu Xiao
Achieving both efficiency and selectivity in nuclease-mimicking nanozymes remains challenging due to the intrinsic coupling between substrate recognition and catalytic activation. Here we report an asymmetric Yb3+/Yb2+ dual-site nuclease mimic (Yb-BDC-Cl) constructed on lanthanide metal–organic frameworks (Ln-MOFs) scaffolds via a hierarchical spatial decoupling strategy. In this architecture, the asymmetric arrangement decouples substrate recognition and catalytic activation: Yb3+ nodes act as Lewis-acidic anchoring sites for phosphate coordination, whereas Yb2+ centers derived from oxygen vacancies serve as redox-active sites for O2-mediated oxidative cleavage. This spatially segregated configuration enables cooperative DNA cleavage with high efficiency and sequence selectivity toward poly(T) sequences (poly T80, half-life ≈ 2.0 h). Mechanistic and structural investigations confirm the coexistence of asymmetric sites and elucidate that Yb3+-mediated substrate anchoring dictates sequence selectivity, whereas Yb2+-assisted O2 activation governs oxidative reactivity. Guided by these insights, we develop a mechanistically validated dual-pathway inhibitory biosensor with self-calibration capability, providing functional evidence for the operational independence of dual sites. Together, these findings establish asymmetric spatial decoupling as a paradigm for constructing highly efficient and sequence-selective artificial nucleases.
{"title":"Constructing Asymmetric Dual-Site Lanthanide MOF for Sequence-Selective DNA Cleavage","authors":"Zhiwen Gan, Long Yu, Yixu Zhou, Yongzhen Liu, Jiyu Tong, Shi Chen, Yuxiu Xiao","doi":"10.1021/acscatal.5c08219","DOIUrl":"https://doi.org/10.1021/acscatal.5c08219","url":null,"abstract":"Achieving both efficiency and selectivity in nuclease-mimicking nanozymes remains challenging due to the intrinsic coupling between substrate recognition and catalytic activation. Here we report an asymmetric Yb<sup>3+</sup>/Yb<sup>2+</sup> dual-site nuclease mimic (Yb-BDC-Cl) constructed on lanthanide metal–organic frameworks (Ln-MOFs) scaffolds via a hierarchical spatial decoupling strategy. In this architecture, the asymmetric arrangement decouples substrate recognition and catalytic activation: Yb<sup>3+</sup> nodes act as Lewis-acidic anchoring sites for phosphate coordination, whereas Yb<sup>2+</sup> centers derived from oxygen vacancies serve as redox-active sites for O<sub>2</sub>-mediated oxidative cleavage. This spatially segregated configuration enables cooperative DNA cleavage with high efficiency and sequence selectivity toward poly(T) sequences (poly T80, half-life ≈ 2.0 h). Mechanistic and structural investigations confirm the coexistence of asymmetric sites and elucidate that Yb<sup>3+</sup>-mediated substrate anchoring dictates sequence selectivity, whereas Yb<sup>2+</sup>-assisted O<sub>2</sub> activation governs oxidative reactivity. Guided by these insights, we develop a mechanistically validated dual-pathway inhibitory biosensor with self-calibration capability, providing functional evidence for the operational independence of dual sites. Together, these findings establish asymmetric spatial decoupling as a paradigm for constructing highly efficient and sequence-selective artificial nucleases.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"74 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072647","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}
Pub Date : 2026-01-29DOI: 10.1021/acscatal.5c08832
Zhongtao Sun, Jielang Huang, Zijie Ji, Kexin Feng, Dongyuan Liu, Chongchong Wu, Yi Zhang
The conversion of CO2 to olefins using iron-based catalysts has garnered significant interest due to its potential in reducing CO2 emissions. Herein, a Na-promoted ZnFe2O4 catalyst exhibits a high CO2 conversion (36.0%) and olefin selectivity (81.0%). Based on the combined results of various characterization techniques, including XPS, Mössbauer spectroscopy, XAS, and DFT calculations, the ZnFe2O4 catalyst induces a relatively electron-deficient state in the χ-Fe5C2 species compared with Zn-promoted iron oxide catalyst, thereby promoting olefin formation during CO2 hydrogenation. DFT calculations show that the ZnFe2O4 catalyst demonstrates a favorable capability for CH2 coupling to form olefins. The Na promoter enhances CO2 adsorption, thereby reducing the H/C ratio on the catalyst surface and promoting the formation of olefins. The synergistic effect between the Na promoter and the relatively electron-deficient χ-Fe5C2 species on the 0.5Na/ZnFe2O4 catalyst results in the highest observed olefin selectivity during CO2 hydrogenation.
{"title":"Revealing the Effects of χ-Fe5C2 Species on CO2 Hydrogenation to Olefins","authors":"Zhongtao Sun, Jielang Huang, Zijie Ji, Kexin Feng, Dongyuan Liu, Chongchong Wu, Yi Zhang","doi":"10.1021/acscatal.5c08832","DOIUrl":"https://doi.org/10.1021/acscatal.5c08832","url":null,"abstract":"The conversion of CO<sub>2</sub> to olefins using iron-based catalysts has garnered significant interest due to its potential in reducing CO<sub>2</sub> emissions. Herein, a Na-promoted ZnFe<sub>2</sub>O<sub>4</sub> catalyst exhibits a high CO<sub>2</sub> conversion (36.0%) and olefin selectivity (81.0%). Based on the combined results of various characterization techniques, including XPS, Mössbauer spectroscopy, XAS, and DFT calculations, the ZnFe<sub>2</sub>O<sub>4</sub> catalyst induces a relatively electron-deficient state in the χ-Fe<sub>5</sub>C<sub>2</sub> species compared with Zn-promoted iron oxide catalyst, thereby promoting olefin formation during CO<sub>2</sub> hydrogenation. DFT calculations show that the ZnFe<sub>2</sub>O<sub>4</sub> catalyst demonstrates a favorable capability for CH<sub>2</sub> coupling to form olefins. The Na promoter enhances CO<sub>2</sub> adsorption, thereby reducing the H/C ratio on the catalyst surface and promoting the formation of olefins. The synergistic effect between the Na promoter and the relatively electron-deficient χ-Fe<sub>5</sub>C<sub>2</sub> species on the 0.5Na/ZnFe<sub>2</sub>O<sub>4</sub> catalyst results in the highest observed olefin selectivity during CO<sub>2</sub> hydrogenation.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"80 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-01-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098125","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}
Pub Date : 2026-01-28DOI: 10.1021/acscatal.5c08855
Mustafa Eid, , , Jin Li, , , Nilanjan Roy, , , Kathryn MacIntosh, , , Michael J. Janik*, , and , Robert M. Rioux*,
Intermetallic compounds serve as model catalysts for selective hydrogenation reactions, offering precise control over the active site composition(s), geometric and electronic structure. The addition of a third element to form a ternary intermetallic alters the exposed crystal facet(s), demonstrating a strategy to impart improved catalytic behavior in intermetallic catalysts. The site-specific substitution of a small fraction of Pd atoms with Au in pyrite-type PdSb2 results in the preferential exposure of the (100) facet over the (111) facet. Electron back scattered diffraction and density functional theory calculations confirm the facet change upon the substitution of Pd with Au to form the ternary Pd1–xAuxSb2 (0.075 ≤ x ≤ 0.25). The (100) facet demonstrates higher net alkene selectivity due to significantly weaker alkene binding compared to the (111) facet. Distinct from our prior work on chemical substitution to directly alter the active site composition, this work demonstrates the indirect modification of active sites via preferential facet exposure.
{"title":"Facet Preferencing by Chemical Substitution Controls Semi-Hydrogenation Selectivity in Ternary Pyrite-Type Intermetallic Compounds","authors":"Mustafa Eid, , , Jin Li, , , Nilanjan Roy, , , Kathryn MacIntosh, , , Michael J. Janik*, , and , Robert M. Rioux*, ","doi":"10.1021/acscatal.5c08855","DOIUrl":"10.1021/acscatal.5c08855","url":null,"abstract":"<p >Intermetallic compounds serve as model catalysts for selective hydrogenation reactions, offering precise control over the active site composition(s), geometric and electronic structure. The addition of a third element to form a ternary intermetallic alters the exposed crystal facet(s), demonstrating a strategy to impart improved catalytic behavior in intermetallic catalysts. The site-specific substitution of a small fraction of Pd atoms with Au in pyrite-type PdSb<sub>2</sub> results in the preferential exposure of the (100) facet over the (111) facet. Electron back scattered diffraction and density functional theory calculations confirm the facet change upon the substitution of Pd with Au to form the ternary Pd<sub>1–<i>x</i></sub>Au<sub><i>x</i></sub>Sb<sub>2</sub> (0.075 ≤ <i>x</i> ≤ 0.25). The (100) facet demonstrates higher net alkene selectivity due to significantly weaker alkene binding compared to the (111) facet. Distinct from our prior work on chemical substitution to directly alter the active site composition, this work demonstrates the indirect modification of active sites via preferential facet exposure.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 3","pages":"2881–2890"},"PeriodicalIF":13.1,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c08855","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057109","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acscatal.5c07042
Irene Barba-Nieto*, , , Marcos Fernández-García, , , Kasala Prabhakar Reddy, , , Yuxi Wang, , , Anna Kubacka, , , Jorge Moncada, , , Guilherme Felipe Lenz, , , Sooyeon Hwang, , , Sanjaya D. Senanayake, , and , José A. Rodriguez*,
This work investigates Ru-CeO2–TiO2 catalysts for the CO2 methanation reaction and compares their performance with that of previously studied Ru-CeO2 systems. Despite the lower Ru loading, the TiO2-containing catalysts exhibit a significantly higher activity. To understand this behavior, in situ X-ray absorption spectroscopy (XAS) was carried out at the Ru K-edge and Ce L3-edge. Unlike Ru-CeO2, which displays the reversible redox behavior of Ru, the Ru-CeO2–TiO2 catalysts show irreversible Ru reduction and a substantially higher fraction of Ce3+ species under all tested conditions (H2, CO2, H2/CO2). The stabilization of metallic Ru during methanation, together with the enhanced formation of Ce3+ promoted by TiO2 through interfacial electronic transfer, accounts for the catalyst’s high activity. Complementary in situ DRIFTS measurements reveal the formation and rapid consumption of bidentate carbonates and formates. These species act as a key intermediate in methane formation. Overall, these findings highlight the crucial role of the mixed CeO2–TiO2 oxide in tuning the surface chemistry of the catalysts by stabilizing metallic Ru, enhancing ceria reducibility, and promoting efficient reaction pathways for CO2 methanation. The manipulation of metal ↔ oxide–oxide interactions can be a very useful tool when dealing with the valorization of CO2.
{"title":"In Situ Studies of Ru-CeO2–TiO2 Catalysts for Selective CO2 Hydrogenation to Methane: Importance of Metal ↔ Oxide–Oxide Interactions","authors":"Irene Barba-Nieto*, , , Marcos Fernández-García, , , Kasala Prabhakar Reddy, , , Yuxi Wang, , , Anna Kubacka, , , Jorge Moncada, , , Guilherme Felipe Lenz, , , Sooyeon Hwang, , , Sanjaya D. Senanayake, , and , José A. Rodriguez*, ","doi":"10.1021/acscatal.5c07042","DOIUrl":"10.1021/acscatal.5c07042","url":null,"abstract":"<p >This work investigates Ru-CeO<sub>2</sub>–TiO<sub>2</sub> catalysts for the CO<sub>2</sub> methanation reaction and compares their performance with that of previously studied Ru-CeO<sub>2</sub> systems. Despite the lower Ru loading, the TiO<sub>2</sub>-containing catalysts exhibit a significantly higher activity. To understand this behavior, in situ X-ray absorption spectroscopy (XAS) was carried out at the Ru K-edge and Ce L<sub>3</sub>-edge. Unlike Ru-CeO<sub>2</sub>, which displays the reversible redox behavior of Ru, the Ru-CeO<sub>2</sub>–TiO<sub>2</sub> catalysts show irreversible Ru reduction and a substantially higher fraction of Ce<sup>3+</sup> species under all tested conditions (H<sub>2</sub>, CO<sub>2</sub>, H<sub>2</sub>/CO<sub>2</sub>). The stabilization of metallic Ru during methanation, together with the enhanced formation of Ce<sup>3+</sup> promoted by TiO<sub>2</sub> through interfacial electronic transfer, accounts for the catalyst’s high activity. Complementary in situ DRIFTS measurements reveal the formation and rapid consumption of bidentate carbonates and formates. These species act as a key intermediate in methane formation. Overall, these findings highlight the crucial role of the mixed CeO<sub>2</sub>–TiO<sub>2</sub> oxide in tuning the surface chemistry of the catalysts by stabilizing metallic Ru, enhancing ceria reducibility, and promoting efficient reaction pathways for CO<sub>2</sub> methanation. The manipulation of metal ↔ oxide–oxide interactions can be a very useful tool when dealing with the valorization of CO<sub>2</sub>.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 3","pages":"2280–2292"},"PeriodicalIF":13.1,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070625","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}
Pub Date : 2026-01-28DOI: 10.1021/acscatal.5c08995
Jiajun Zhang, , , Ru-Han A, , , Chao Xu, , and , Xiao-Feng Wu*,
Copper catalysis offers an attractive earth-abundant alternative to noble-metal-based carbonylation, yet its application to aryl electrophiles remains severely limited due to the low redox flexibility of Cu(I) and the inhibiting effect of CO coordination. Here we report a photocatalyst-free strategy that overcomes these intrinsic limitations by exploiting in situ generated NHC-stabilized aryl-Cu(I) complexes as bifunctional catalytic species capable of both light absorption and aryl-group transfer. This platform enables the development of copper-catalyzed carbonylation of arylboronic esters using aryl thianthrenium salts as electrophilic coupling partners. The method exhibits a broad substrate scope and high functional-group compatibility, accommodating diverse electron-rich and electron-deficient aromatics as well as structurally complex late-stage scaffolds. This work introduces a generalizable design principle for activating aryl electrophiles under copper catalysis and establishes a dual-functional reactivity mode for Cu(I) species in carbonylation chemistry.
{"title":"Photoinduced Copper-Catalyzed Carbonylation of Arylthianthrenium Salts with Aryl Boronates toward Ketones","authors":"Jiajun Zhang, , , Ru-Han A, , , Chao Xu, , and , Xiao-Feng Wu*, ","doi":"10.1021/acscatal.5c08995","DOIUrl":"10.1021/acscatal.5c08995","url":null,"abstract":"<p >Copper catalysis offers an attractive earth-abundant alternative to noble-metal-based carbonylation, yet its application to aryl electrophiles remains severely limited due to the low redox flexibility of Cu(I) and the inhibiting effect of CO coordination. Here we report a photocatalyst-free strategy that overcomes these intrinsic limitations by exploiting <i>in situ</i> generated NHC-stabilized aryl-Cu(I) complexes as bifunctional catalytic species capable of both light absorption and aryl-group transfer. This platform enables the development of copper-catalyzed carbonylation of arylboronic esters using aryl thianthrenium salts as electrophilic coupling partners. The method exhibits a broad substrate scope and high functional-group compatibility, accommodating diverse electron-rich and electron-deficient aromatics as well as structurally complex late-stage scaffolds. This work introduces a generalizable design principle for activating aryl electrophiles under copper catalysis and establishes a dual-functional reactivity mode for Cu(I) species in carbonylation chemistry.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 3","pages":"1958–1965"},"PeriodicalIF":13.1,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c08995","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070626","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-28DOI: 10.1021/acscatal.5c06829
Baraa Werghi*, , , Benjamin M. Moskowitz, , , Libor Kovarik, , , Mark Bowden, , , Oliva M. Primera-Pedrozo, , and , Janos Szanyi*,
Controlling the dynamic mobility of catalyst surface active sites and their interactions with the surrounding environment is critical in generating active surfaces that directly influence catalytic activity and selectivity. Here, we report a strategy for tailoring the dispersion and electronic environment of single-atom Rh catalysts by decorating the alumina support with highly dispersed (HD) cerium and molybdenum oxides. The resulting catalysts exhibit markedly different behaviors in the Reverse Water–Gas Shift (RWGS) reaction. In particular, Rh/MoOx(HD)/Al2O3 maintains atomically dispersed Rh even at elevated temperatures (up to 400 °C), achieving CO selectivity of up to 100% and resisting sintering via the formation of a newly developed structure featuring Rh single atoms embedded in MoOx clusters. In situ spectroscopy and microscopy analyses confirm the stabilization of Rh and the dynamic evolution of the Rh–Mo coordination under the reaction conditions. Our findings highlight the power of support modification in steering active site structure and activity, offering a pathway toward enhanced performance and tunable single-atom catalysts for CO2 valorization.
{"title":"Tuning the Coordination Environment of Rh Single Atoms on Highly Dispersed Reducible Oxides for Enhanced Reverse Water–Gas Shift Performance","authors":"Baraa Werghi*, , , Benjamin M. Moskowitz, , , Libor Kovarik, , , Mark Bowden, , , Oliva M. Primera-Pedrozo, , and , Janos Szanyi*, ","doi":"10.1021/acscatal.5c06829","DOIUrl":"10.1021/acscatal.5c06829","url":null,"abstract":"<p >Controlling the dynamic mobility of catalyst surface active sites and their interactions with the surrounding environment is critical in generating active surfaces that directly influence catalytic activity and selectivity. Here, we report a strategy for tailoring the dispersion and electronic environment of single-atom Rh catalysts by decorating the alumina support with highly dispersed (HD) cerium and molybdenum oxides. The resulting catalysts exhibit markedly different behaviors in the Reverse Water–Gas Shift (RWGS) reaction. In particular, Rh/MoO<sub><i>x</i></sub>(HD)/Al<sub>2</sub>O<sub>3</sub> maintains atomically dispersed Rh even at elevated temperatures (up to 400 °C), achieving CO selectivity of up to 100% and resisting sintering via the formation of a newly developed structure featuring Rh single atoms embedded in MoO<sub><i>x</i></sub> clusters. <i>In situ</i> spectroscopy and microscopy analyses confirm the stabilization of Rh and the dynamic evolution of the Rh–Mo coordination under the reaction conditions. Our findings highlight the power of support modification in steering active site structure and activity, offering a pathway toward enhanced performance and tunable single-atom catalysts for CO<sub>2</sub> valorization.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 3","pages":"2258–2267"},"PeriodicalIF":13.1,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146070624","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}
Pub Date : 2026-01-28DOI: 10.1021/acscatal.5c08799
Jiejie Ling, Jilong Wang, Yao Xiao, Yan Gao, Xudong Tian, Jie Tuo, Chuang Liu, Dunru Zhu, Jingang Jiang, Shipeng Ding, Jian Li, Zhendong Wang, Anmin Zheng, Peng Wu, Le Xu
The conversion of CO2 to hydrocarbons via the methanol-mediated pathway represents a crucial route for carbon neutrality, yet preferable production of more value-added light olefins remains constrained by the fundamental activity-selectivity trade-off in zeolite catalysts. While previous studies established an acidity regulation mechanism based on balancing acid density with acid strength, the conversion of methanol intermediates is also critically governed by their intracrystalline diffusion, which can be severely hindered by structural defects particularly prevalent in highly siliceous zeolites. This work demonstrates a different approach that synergistically integrates zeolite acidity and defect engineering. A hydrothermal synthesis strategy with a selected inorganic source precisely controls aluminum incorporation into the highly siliceous CHA zeolite framework (Si/Al > 800). Subsequently, a postsynthetic fluorination followed by calcination effectively heals silanol defects. The resulting HS-CHA-F zeolite features a hydrophobic framework that facilitates rapid methanol diffusion while utilizing precisely tuned ultraweak acidity to steer selective C–C coupling. The optimized OXZEO bifunctional catalyst ZnZrOx/HS-CHA-F achieves 38.5% CO2 conversion and 91.3% light olefin selectivity in hydrocarbons at 653 K and 4 MPa, substantially outperforming conventional SSZ-13 and SAPO-34 benchmarks. This study establishes a generalizable method for overcoming long-standing limitations in CO2 hydrogenation through coupled zeolite acidity and defect engineering.
{"title":"Tailoring Defects in Highly Siliceous CHA-Type Zeolite for Enhanced CO2 Hydrogenation to Light Olefins","authors":"Jiejie Ling, Jilong Wang, Yao Xiao, Yan Gao, Xudong Tian, Jie Tuo, Chuang Liu, Dunru Zhu, Jingang Jiang, Shipeng Ding, Jian Li, Zhendong Wang, Anmin Zheng, Peng Wu, Le Xu","doi":"10.1021/acscatal.5c08799","DOIUrl":"https://doi.org/10.1021/acscatal.5c08799","url":null,"abstract":"The conversion of CO<sub>2</sub> to hydrocarbons via the methanol-mediated pathway represents a crucial route for carbon neutrality, yet preferable production of more value-added light olefins remains constrained by the fundamental activity-selectivity trade-off in zeolite catalysts. While previous studies established an acidity regulation mechanism based on balancing acid density with acid strength, the conversion of methanol intermediates is also critically governed by their intracrystalline diffusion, which can be severely hindered by structural defects particularly prevalent in highly siliceous zeolites. This work demonstrates a different approach that synergistically integrates zeolite acidity and defect engineering. A hydrothermal synthesis strategy with a selected inorganic source precisely controls aluminum incorporation into the highly siliceous CHA zeolite framework (Si/Al > 800). Subsequently, a postsynthetic fluorination followed by calcination effectively heals silanol defects. The resulting HS-CHA-F zeolite features a hydrophobic framework that facilitates rapid methanol diffusion while utilizing precisely tuned ultraweak acidity to steer selective C–C coupling. The optimized OXZEO bifunctional catalyst ZnZrO<sub><i>x</i></sub>/HS-CHA-F achieves 38.5% CO<sub>2</sub> conversion and 91.3% light olefin selectivity in hydrocarbons at 653 K and 4 MPa, substantially outperforming conventional SSZ-13 and SAPO-34 benchmarks. This study establishes a generalizable method for overcoming long-standing limitations in CO<sub>2</sub> hydrogenation through coupled zeolite acidity and defect engineering.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"24 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072537","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}
Electrooxidation reaction of ethylene glycol (EG) offers an efficient route for producing value-added chemicals (glycolic acid (GA)) and facilitates coupled hydrogen (H2) production. However, its practical performance is often hindered by sluggish reaction kinetics and catalyst deactivation, both of which are strongly influenced by interfacial microenvironments. Here, we report an interfacial engineering strategy that employs polydopamine (PDA) to modulate the hydrogen-bonding network at the Au catalyst-electrolyte interface, which mitigates the oxidative deactivation of Au, achieving a 1.78-fold enhancement for electrooxidation of EG-to-GA compared with the pure Au catalyst (0.41 vs 0.23 mmol cm–2 h–1 at 1.5 V vs RHE). Mechanistic studies reveal that Au sites generate reactive OH* species to drive EG oxidation, and the PDA layer enriches EG near active sites. Moreover, PDA can regulate the interfacial hydrogen-bonding network, that is, generating strong hydrogen bonding with EG disrupts the tetrahedral water network, generating a more open and dynamic hydration environment that facilitates EG adsorption and activation. When integrated into a flow-cell electrolyzer, Au/PDA catalyst delivers efficient coproduction of glycolic acid (3.0 mmol h–1) and hydrogen (8.1 mmol h–1) with high selectivity under a 0.8 V operating voltage. This work elucidates a molecular-level mechanism for hydrogen-bond-mediated interfacial regulation and establishes a general design principle for enhancing alcohol electrooxidation through adaptive hydrogen-bonding engineering.
乙二醇(EG)的电氧化反应为生产高附加值化学品(乙醇酸(GA))提供了一条有效的途径,并促进了偶联氢(H2)的产生。然而,它的实际性能往往受到反应动力学缓慢和催化剂失活的阻碍,这两者都受到界面微环境的强烈影响。在这里,我们报道了一种界面工程策略,该策略使用聚多巴胺(PDA)来调节Au催化剂-电解质界面的氢键网络,从而减轻Au的氧化失活,与纯Au催化剂相比,eg到ga的电氧化增强了1.78倍(在1.5 V vs RHE下为0.41 vs 0.23 mmol cm-2 h-1)。机制研究表明,Au位点产生活性OH*驱动EG氧化,PDA层富集活性位点附近的EG。此外,PDA可以调节界面氢键网络,即与EG产生强氢键,破坏四面体水网络,产生更加开放和动态的水化环境,有利于EG的吸附和活化。当集成到流动电池电解槽中时,Au/PDA催化剂在0.8 V的工作电压下具有高选择性地高效协同生产乙醇酸(3.0 mmol h-1)和氢气(8.1 mmol h-1)。这项工作阐明了氢键介导的界面调节的分子水平机制,并建立了通过自适应氢键工程增强醇电氧化的一般设计原则。
{"title":"Hydrogen-Bonding Network Modulation via Polydopamine Enabling Efficient Ethylene Glycol Electrooxidation","authors":"Lilai Sun, , , Yifan Yan, , , Qinghui Ren*, , , Yanchun Xu, , , Yu Fu, , , Zhidong Wang, , , Zhenhua Li*, , and , Mingfei Shao*, ","doi":"10.1021/acscatal.5c08621","DOIUrl":"10.1021/acscatal.5c08621","url":null,"abstract":"<p >Electrooxidation reaction of ethylene glycol (EG) offers an efficient route for producing value-added chemicals (glycolic acid (GA)) and facilitates coupled hydrogen (H<sub>2</sub>) production. However, its practical performance is often hindered by sluggish reaction kinetics and catalyst deactivation, both of which are strongly influenced by interfacial microenvironments. Here, we report an interfacial engineering strategy that employs polydopamine (PDA) to modulate the hydrogen-bonding network at the Au catalyst-electrolyte interface, which mitigates the oxidative deactivation of Au, achieving a 1.78-fold enhancement for electrooxidation of EG-to-GA compared with the pure Au catalyst (0.41 vs 0.23 mmol cm<sup>–2</sup> h<sup>–1</sup> at 1.5 V vs RHE). Mechanistic studies reveal that Au sites generate reactive OH* species to drive EG oxidation, and the PDA layer enriches EG near active sites. Moreover, PDA can regulate the interfacial hydrogen-bonding network, that is, generating strong hydrogen bonding with EG disrupts the tetrahedral water network, generating a more open and dynamic hydration environment that facilitates EG adsorption and activation. When integrated into a flow-cell electrolyzer, Au/PDA catalyst delivers efficient coproduction of glycolic acid (3.0 mmol h<sup>–1</sup>) and hydrogen (8.1 mmol h<sup>–1</sup>) with high selectivity under a 0.8 V operating voltage. This work elucidates a molecular-level mechanism for hydrogen-bond-mediated interfacial regulation and establishes a general design principle for enhancing alcohol electrooxidation through adaptive hydrogen-bonding engineering.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 3","pages":"2789–2799"},"PeriodicalIF":13.1,"publicationDate":"2026-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146057108","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}
Pub Date : 2026-01-27DOI: 10.1021/acscatal.5c08789
Spencer Gardiner, , , Joseph Talley, , , Tyler Green, , , Christopher Haynie, , , Corbyn Kubalek, , , Matthew Argyle, , , William Heaps, , , Joshua Ebbert, , , Deon Allen, , , Dallin Chipman, , , Bradley C Bundy*, , and , Dennis Della Corte*,
Engineered luciferases have transformed biological imaging and sensing, yet optimizing NanoLuc luciferase (NLuc) remains challenging due to the inherent stability-activity trade-off and its limited sequence homology with characterized proteins. We report a hybrid approach that synergistically integrates deep learning with structure-guided rational design to develop enhanced NLuc variants that improve thermostability and thereby activity at elevated temperatures. By systematically analyzing libraries of engineered variants, we established that modifications to termini and loops distal from the catalytic center, combined with preservation of allosterically coupled networks, effectively increase thermal resilience while maintaining enzymatic function. Our optimized variants─notably B.07 and B.09─exhibit substantial thermostability enhancements (increased melting temperatures of 7.2 and 5.1 °C, respectively), leading to the sustained activity of a high-activity mutant at elevated temperatures. Molecular dynamics simulations and protein folding studies elucidate how these mutations favorably modulate conformational landscapes without perturbing the substrate binding architecture. Beyond providing a thermostabilized tool for bioluminescence applications, our integrated methodology presents a framework for engineering enzymes when traditional homology-based approaches fail and stability-activity constraints present formidable barriers to improvement.
{"title":"Advancing NanoLuc Luciferase Stability beyond Directed Evolution and Rational Design through Expert-Guided Deep Learning","authors":"Spencer Gardiner, , , Joseph Talley, , , Tyler Green, , , Christopher Haynie, , , Corbyn Kubalek, , , Matthew Argyle, , , William Heaps, , , Joshua Ebbert, , , Deon Allen, , , Dallin Chipman, , , Bradley C Bundy*, , and , Dennis Della Corte*, ","doi":"10.1021/acscatal.5c08789","DOIUrl":"10.1021/acscatal.5c08789","url":null,"abstract":"<p >Engineered luciferases have transformed biological imaging and sensing, yet optimizing NanoLuc luciferase (NLuc) remains challenging due to the inherent stability-activity trade-off and its limited sequence homology with characterized proteins. We report a hybrid approach that synergistically integrates deep learning with structure-guided rational design to develop enhanced NLuc variants that improve thermostability and thereby activity at elevated temperatures. By systematically analyzing libraries of engineered variants, we established that modifications to termini and loops distal from the catalytic center, combined with preservation of allosterically coupled networks, effectively increase thermal resilience while maintaining enzymatic function. Our optimized variants─notably B.07 and B.09─exhibit substantial thermostability enhancements (increased melting temperatures of 7.2 and 5.1 °C, respectively), leading to the sustained activity of a high-activity mutant at elevated temperatures. Molecular dynamics simulations and protein folding studies elucidate how these mutations favorably modulate conformational landscapes without perturbing the substrate binding architecture. Beyond providing a thermostabilized tool for bioluminescence applications, our integrated methodology presents a framework for engineering enzymes when traditional homology-based approaches fail and stability-activity constraints present formidable barriers to improvement.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 3","pages":"2849–2860"},"PeriodicalIF":13.1,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acscatal.5c08789","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048306","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-27DOI: 10.1021/acscatal.5c09147
Sutao Lin, , , Dongdong Qiao, , , Tengyu Gao, , , Rui Xiong, , , Lulu Chen, , , Jun Chen*, , and , Sen Lin*,
Subsurface hydrogen transport in alloys offers poison resistance and enhanced adsorption capacity compared to surface-mediated processes, yet its underlying dynamic mechanisms remain largely elusive. Herein, we employ machine learning-accelerated molecular dynamics simulations to investigate atomic-scale hydrogen spillover dynamics in Pt1/Ag single-atom near-surface alloys. We identify two distinct penetration pathways: a H–H collision-induced mechanism, where impulsive interactions between dissociated H atoms at the Pt1 site transiently enhance the vertical kinetic energy of one atom, enabling barrier overcoming and subsurface entry; and a surface spillover-mediated mechanism, involving initial hopping of hydrogen species across Ag sites coupled with stabilization from subsurface Pt atoms that collectively facilitate subsequent penetration. In addition, subsurface diffusion shows higher mobility and a stronger temperature response than surface diffusion. These findings provide fundamental insights into subsurface hydrogen transport and establish design principles for advanced catalytic and hydrogen storage systems through subsurface engineering.
{"title":"Unraveling Subsurface Hydrogen Spillover Dynamics in Pt1/Ag(111) Single-Atom Near-Surface Alloys","authors":"Sutao Lin, , , Dongdong Qiao, , , Tengyu Gao, , , Rui Xiong, , , Lulu Chen, , , Jun Chen*, , and , Sen Lin*, ","doi":"10.1021/acscatal.5c09147","DOIUrl":"10.1021/acscatal.5c09147","url":null,"abstract":"<p >Subsurface hydrogen transport in alloys offers poison resistance and enhanced adsorption capacity compared to surface-mediated processes, yet its underlying dynamic mechanisms remain largely elusive. Herein, we employ machine learning-accelerated molecular dynamics simulations to investigate atomic-scale hydrogen spillover dynamics in Pt<sub>1</sub>/Ag single-atom near-surface alloys. We identify two distinct penetration pathways: a H–H collision-induced mechanism, where impulsive interactions between dissociated H atoms at the Pt<sub>1</sub> site transiently enhance the vertical kinetic energy of one atom, enabling barrier overcoming and subsurface entry; and a surface spillover-mediated mechanism, involving initial hopping of hydrogen species across Ag sites coupled with stabilization from subsurface Pt atoms that collectively facilitate subsequent penetration. In addition, subsurface diffusion shows higher mobility and a stronger temperature response than surface diffusion. These findings provide fundamental insights into subsurface hydrogen transport and establish design principles for advanced catalytic and hydrogen storage systems through subsurface engineering.</p>","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"16 3","pages":"2910–2917"},"PeriodicalIF":13.1,"publicationDate":"2026-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146048307","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}