Chinese Journal of Catalysis最新文献_第2页

Achieving selective C−O bond cleavage of esters over monolayer NiMoS catalysts derived from oil-soluble polyoxometalates 在油溶性多金属氧酸盐衍生的单层NiMoS催化剂上实现酯类C−O键的选择性裂解

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65104-2

Chongzheng Xu, Haoping Di, Fengyue Sun, Wenjing Bao, Yanwei Ju, Dengwei Yan, Changle Yue, Yiyuan Xu, Yunxiu Zhao, Shuo Wang, Jiqian Wang, Yukun Lu

{"title":"Achieving selective C−O bond cleavage of esters over monolayer NiMoS catalysts derived from oil-soluble polyoxometalates","authors":"Chongzheng Xu, Haoping Di, Fengyue Sun, Wenjing Bao, Yanwei Ju, Dengwei Yan, Changle Yue, Yiyuan Xu, Yunxiu Zhao, Shuo Wang, Jiqian Wang, Yukun Lu","doi":"10.1016/S1872-2067(26)65104-2","DOIUrl":"10.1016/S1872-2067(26)65104-2","url":null,"abstract":"<div><div>Sulfided NiMo catalysts can effectively hydrogenate oxygen-rich bio-oils into high quality hydrocarbon fuels. However, precisely controlling the cleavage of C−O bonds remains challenging. Here, we synthesized an oil-soluble precursor NiMo6-DODA by encapsulating the polyoxometalates (POMs) (NH4)4[NiMo6O24H6] (NiMo6) with surfactants, followed by in-situ construction of an ultra-dispersed monolayer NiMoS catalyst. The “surfactant shell” of the precursor ensured its homogeneous dispersion in the oil phase, while gradually sacrificing and decomposing during the sulfidation to mitigate the aggregation of the MoS2 nanosheets. Meanwhile, the well-defined “POMs core” established an atomic-level Ni-Mo proximity, ensuring the dominance of the Ni-promoted MoS2 active phase. This design not only altered the adsorption configuration of esters on the NiMo catalyst but also introduced abundant edge sulfur vacancies to promote oxygen atom adsorption and accelerate C−O bond cleavage. The results showed that NiMo6-DODA achieved 100% conversion of methyl palmitate and 100% alkane selectivity under low catalyst loading conditions. Notably, the selectivity for n-hexadecane reached 94.2%, significantly surpassing that obtained with a commercial oil-soluble precursor (69.8%). Furthermore, the catalyst maintained high activity across multiple reaction cycles and in the solvent-free conversion of real bio-oils. This strategy of pre-assembly combined with sacrificial sulfidation provides a simple and effective route for designing hydrodeoxygenation catalysts that enable precise control over ester C−O bond cleavage.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"87 ","pages":"Pages 327-341"},"PeriodicalIF":17.2,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652143","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

Efficient solar-simulated-driven valorization of non-edible oils for biodiesel production via interfacial localized photothermal catalysis 通过界面局部光热催化，太阳能模拟驱动的生物柴油生产中非食用油的高效增值

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65087-5

Heng Zhou, Longfei Hong, Yan Zhang, Yuyue Zhou, Sheng Chu, Huiyan Zhang, Hui Li, Tianyi Ma, Heng Zhang

{"title":"Efficient solar-simulated-driven valorization of non-edible oils for biodiesel production via interfacial localized photothermal catalysis","authors":"Heng Zhou, Longfei Hong, Yan Zhang, Yuyue Zhou, Sheng Chu, Huiyan Zhang, Hui Li, Tianyi Ma, Heng Zhang","doi":"10.1016/S1872-2067(26)65087-5","DOIUrl":"10.1016/S1872-2067(26)65087-5","url":null,"abstract":"<div><div>Harnessing solar energy as a power source for sustainable fuel production from biomass waste presents an effective solution to energy and environmental challenges. However, efficient utilization of low-energy near-infrared (NIR) light (representing ~50% of solar irradiance) continues a critical bottleneck especially for non-edible oils valorization. Here, we report a cellulose-derived sulfonated hydrochar (PC-SO3H-1) utilizing the full solar spectrum for highly efficient biodiesel production, achieving a remarkable biodiesel yield of 98.29% within only 30 min, which far exceeds the theoretical limit. Favorable NIR absorption of narrow bandgap PC-SO3H-1 combined with substrate adsorption capacity enhanced by -SO3H functionalization overcomes thermodynamic equilibrium limitations. The optimized charge transfer dynamics accelerate the interfacial localized photothermal effect, driving the esterification reaction forward while minimizing heat loss and significantly enhancing the utilization of NIR photons. Density functional theory calculations demonstrate the formation of crucial intermediate ester carbonyl groups (C=O), with PC-SO3H-1 effectively reducing the activation energy barrier associated with the rate-limiting process. This sustainable noble metal-free photothermal catalytic system of high-efficiency overcomes the reliance of traditional photocatalysis on high-energy photons, offering novel insights into the full spectrum solar-driven production of green and renewable biofuels.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"87 ","pages":"Pages 156-169"},"PeriodicalIF":17.2,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148660819","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

Hydroxymethylation of alkynes with N-methylamines and water enabled by Co/photoredox dual catalysis Co/光氧化还原双催化使炔与n -甲胺和水发生羟甲基化

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65076-0

Yan-Lin Li, Ning-Xin Guo, Jia-Ting Bi, Ling-Yu Xue, Yue-Lu Zhu, You-Dong Shao, Ji-Bao Xia

引用次数: 0

Tweaking the electron push-pull effect of vinylene-linked thienothiophene covalent organic frameworks for enhanced selective photocatalysis 调整乙烯连接噻吩共价有机框架的电子推拉效应以增强选择性光催化

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65102-9

Keke Zhang, Fulin Zhang, Yuexin Wang, Fengwei Huang, Kanghui Xiong, Xiang-Kui Gu, Xianjun Lang

{"title":"Tweaking the electron push-pull effect of vinylene-linked thienothiophene covalent organic frameworks for enhanced selective photocatalysis","authors":"Keke Zhang, Fulin Zhang, Yuexin Wang, Fengwei Huang, Kanghui Xiong, Xiang-Kui Gu, Xianjun Lang","doi":"10.1016/S1872-2067(26)65102-9","DOIUrl":"10.1016/S1872-2067(26)65102-9","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) unveil exceptional potential for selective photocatalysis, owing to their molecularly tunable structures. Herein, four COFs are designed with vinylene-linked isomeric thienothiophenes. Thereby, the condensation of 4,7-bis(2,6-dimethylpyridin-4-yl)benzo[c] [1, 2, 5]thiadiazole (MPBTD) and 4,7-bis(2,6-dimethylpyridin-4-yl)benzo[c][1, 2, 5]oxadiazole (MPBO) with thieno[3,2-b]thiophene-2,5-dicarbaldehyde (T32T) and thieno[2,3-b]thiophene- 2,5-dicarbaldehyde (T23T) yields MPBTD-T32T-COF, MPBTD-T23T-COF, MPBO-T32T-COF, and MPBO-T23T-COF, respectively. Comprehensive characterizations and theoretical calculations confirm the well-defined crystalline porous structures and distinct optoelectronic properties of these four COFs. Notably, the electron-withdrawing units, benzo[c][1, 2, 5]thiadiazole and benzo[c][1, 2, 5]oxadiazole, tweak the electron push-pull effect of COFs, leading to distinct photocatalytic performances. In the selective photocatalytic oxidation of three sulfide substrates, the observed performance exhibits the following order: MPBTD-T32T-COF > MPBTD-T23T-COF > MPBO-T32T-COF > MPBO-T23T-COF. Mechanistic studies reveal that superoxide is the predominant reactive oxygen species powering the selective photocatalytic sulfoxidation over MPBTD-T32T-COF. Furthermore, MPBTD-T32T-COF demonstrates recyclability and broad substrate applicability for the selective photocatalytic sulfoxidation.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"87 ","pages":"Pages 206-216"},"PeriodicalIF":17.2,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148651901","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

Subangstrom spatial regulation of Fe1-N4 coordination structure for remarkably efficient C−H bond oxidation Fe1-N4配位结构的亚埃空间调控对C−H键的高效氧化

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65096-6

Jianglin Duan, Pengcheng Deng, Huifeng Xiong, Na Yang, Xueling Zhou, Jingwen Wang, Rui Zhang, Dan Feng, Ji Yang, Yong Qin, Yujing Ren

{"title":"Subangstrom spatial regulation of Fe1-N4 coordination structure for remarkably efficient C−H bond oxidation","authors":"Jianglin Duan, Pengcheng Deng, Huifeng Xiong, Na Yang, Xueling Zhou, Jingwen Wang, Rui Zhang, Dan Feng, Ji Yang, Yong Qin, Yujing Ren","doi":"10.1016/S1872-2067(26)65096-6","DOIUrl":"10.1016/S1872-2067(26)65096-6","url":null,"abstract":"<div><div>Structural regulation of heterogeneous active centers has been widely explored at the nano- and atomic-level, yet achieving subangstrom precision remains highly challenging. Here, we demonstrate subangstrom spatial regulation of the Fe−N bond within a fully uniform Fe1-N4 coordination structure. Strikingly, a 0.1 Å bond compression led to nearly a 23-fold enhancement in C−H bond oxidation. Advanced characterizations confirmed the uniform low-spin Fe1-N4 configuration, with the Fe−N bond distance gradually decreasing from 2.03 to 1.93 Å during pyrolysis. This subtle structural modification originates from the concerted effect of temperature- and curvature-induced distortion on the curved carbon surface, as further supported by theoretical simulations. The Fe−N bond distance was found to govern the electronic structure of the Fe center, where compressed coordination promotes electron accumulation. This structural modulation directly results in the high capability for peroxide group activation on Fe1 single atoms, which affords outstanding C−H bond oxidation, comparable to supported noble metal catalysts. This study provides the experimental demonstration of structural regulation at subangstrom scale, extending the concept of “precise chemistry” in catalyst design from the nano- and atomic- to the subangstrom scale.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"87 ","pages":"Pages 305-315"},"PeriodicalIF":17.2,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148651906","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

Bioinspired acetate-mediated proton shuttling toward robust oxygen evolution 生物激发醋酸盐介导的质子穿梭向强大的氧演化

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65072-3

Jianping Zhang, Kun Zhang, Yinglong Weng, Nannan Li, Tingting Huang, Yitong Lu, Tingyu Sun, Xiaotong Han, Jieshan Qiu

{"title":"Bioinspired acetate-mediated proton shuttling toward robust oxygen evolution","authors":"Jianping Zhang, Kun Zhang, Yinglong Weng, Nannan Li, Tingting Huang, Yitong Lu, Tingyu Sun, Xiaotong Han, Jieshan Qiu","doi":"10.1016/S1872-2067(26)65072-3","DOIUrl":"10.1016/S1872-2067(26)65072-3","url":null,"abstract":"<div><div>Persistent proton accumulation from extensive reactant deprotonation during oxygen evolution reaction (OER) induces severe local acidification at electrode-electrolyte interface, accelerating catalyst degradation and performance decay. Employing NiFe layered double hydroxide (NiFe-LDH) as a model, we present a bioinspired strategy wherein Lewis-basic acetate anion (CH3COO–, Ac–) functions as dynamic proton shuttle to regulate interfacial microenvironment (Ac–-LDH). Ac– undergoes reversible –COO–/–COOH cycle upon protonation, promoting efficient proton transfer and reinforcing hydrogen-bond networks that expedite OH– delivery to LDH surface. Simultaneously, Ac– lone pairs selectively coordinate with Fe centers in LDH framework, tuning electronic structure and enhancing intrinsic activity. In-situ Raman and infrared spectroscopy capture transient CH3COOH formation, while differential electrochemical mass spectrometry evidences proton shuttling via CH3COOD detection. Theoretical calculations reveal that Ac– coordination stabilizes active site and reduces OER energy barrier. Leveraging this dual functionality, Ac–-LDH exhibits superior activity with 213 mV overpotential at 10 mA cm–2 and remarkable durability, maintaining 50 mA cm–2 for over 1200 h in anion-exchange membrane electrolyzer. This work establishes bioinspired molecular shuttles for interfacial microenvironment engineering as versatile paradigm for developing OER catalysts with high activity and durability.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"87 ","pages":"Pages 282-294"},"PeriodicalIF":17.2,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148651908","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

Coking-resistant CeAlO3-Socketed Nickel Nanocatalysts for dry reforming of methane 甲烷干重整用抗焦化cealo3嵌套镍纳米催化剂

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65063-2

Zhongchen Ma, Meiyi Yin, Run Xu, Rongjun Zhang, Tian Lan, Wenli Gu, Guoqing Chen, Yong Lu

{"title":"Coking-resistant CeAlO3-Socketed Nickel Nanocatalysts for dry reforming of methane","authors":"Zhongchen Ma, Meiyi Yin, Run Xu, Rongjun Zhang, Tian Lan, Wenli Gu, Guoqing Chen, Yong Lu","doi":"10.1016/S1872-2067(26)65063-2","DOIUrl":"10.1016/S1872-2067(26)65063-2","url":null,"abstract":"<div><div>Nickel-based catalysts are regarded as the most promising candidates for industrial dry reforming of methane (DRM), yet severe coking and metal sintering impede their commercial viability. Herein, we report a CeAlO3-socketed Ni nanocatalyst with extensive Ni-CeAlO3 interfaces, demonstrating coke-free stability with no deactivation over 500 h test at 700 °C for a feed of CH4/CO2 = 1/1 (undiluted). The socket-structured catalyst was obtained via H2-reduction-triggered Ni exsolution and simultaneous formation of CeAlO3 from a Ce1Al0.95Ni0.05Ox composite oxide. A socketed structure featuring extensive Ni-CeAlO3 interface was achieved upon reduction at 750 °C, which essentially modulated the catalytic activation kinetics of both CO2 and CH4. In-situ diffused reflectance infrared Fourier transformed spectroscopy and isotope-labeling experiments were performed to gain insight into the interfacial catalysis, revealing that CO2 was preferentially activated at the Ni-CeAlO3 interface to form CO and O*, and CH4 was subsequently oxidized by O* to form H2 and another CO through formation of CH3O* intermediates. Such tandem reaction pathway led to stoichiometric conversion of CO2 and CH4 molecules thereby imparting our catalyst to high coking resistance. Our findings shed light on the rational design of a valid Ni-based DRM catalyst with substantial potential for industrial application.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"87 ","pages":"Pages 363-375"},"PeriodicalIF":17.2,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652131","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

Asymmetric N-Ru-S dipole within covalent organic framework enhances internal electric field for efficient CO2 photoreduction 共价有机框架内的不对称N-Ru-S偶极子增强了有效光还原CO2的内部电场

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65082-6

Yueling Chen, Yuling Lin, Ziyan Chen, Xiangyu Kong, Jinhong Bi, Guocheng Huang, Ling Wu

{"title":"Asymmetric N-Ru-S dipole within covalent organic framework enhances internal electric field for efficient CO2 photoreduction","authors":"Yueling Chen, Yuling Lin, Ziyan Chen, Xiangyu Kong, Jinhong Bi, Guocheng Huang, Ling Wu","doi":"10.1016/S1872-2067(26)65082-6","DOIUrl":"10.1016/S1872-2067(26)65082-6","url":null,"abstract":"<div><div>Asymmetric electron distribution at single-atom centers offers a promising pathway to enhance photocatalytic CO2-to-CO conversion; however, direct visualization of how such symmetry-breaking influences local electric fields and reaction coordinates remains elusive. Herein, an asymmetric N-Ru-S motif was constructed in a thiophene-based covalent organic framework (Ru/Py-bTDC) via post-synthetic metalation. Under visible light in a gas-solid system without sacrificial agents, Ru10/Py-bTDC exhibited a CO production of 226.88 μmol·L–1, representing a 13-fold increase over pristine Py-bTDC. In-situ Kelvin probe force microscopy revealed that the N-Ru-S unit acts as a directional nanoscale dipole, intensifying the internal electric field (IEF) by 6.15-fold and steering photogenerated electrons toward Ru sites to facilitate charge separation. In-situ Fourier transform infrared spectroscopy and theoretical calculations demonstrated that the enhanced IEF promotes CO2 activation, lowering the energy barrier for *COOH formation from 2.63 to 0.40 eV and shifting the rate-determining step to *CO desorption. This work establishes a direct spatial correlation between atomic-scale asymmetry, IEF enhancement, and optimized reaction kinetics, offering a design strategy to overcome both charge separation and activation barriers in CO2 photoreduction through symmetry-breaking coordination.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"87 ","pages":"Pages 59-69"},"PeriodicalIF":17.2,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652096","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

High-pressure switch: Redirecting CO2 hydrogenation from hydrocarbons to carboxylic acids and alcohols 高压开关：重定向二氧化碳氢化从碳氢化合物到羧酸和醇

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65097-8

Jiyeon Lee, Muhammad Irshad, Wonjoong Yoon, Jaehoon Kim

{"title":"High-pressure switch: Redirecting CO2 hydrogenation from hydrocarbons to carboxylic acids and alcohols","authors":"Jiyeon Lee, Muhammad Irshad, Wonjoong Yoon, Jaehoon Kim","doi":"10.1016/S1872-2067(26)65097-8","DOIUrl":"10.1016/S1872-2067(26)65097-8","url":null,"abstract":"<div><div>The selective conversion of CO2 into value-added chemicals remains a critical challenge in heterogeneous catalysis. Here, we demonstrate that reaction pressure governs a decisive mechanistic switch in CO2 hydrogenation over potassium-promoted iron catalysts. Catalytic tests conducted from 0.1 to 10.0 MPa reveal that moderate pressure (3.5 MPa) favors Fischer-Tropsch-type pathways, yielding long-chain hydrocarbons through Fe5C2-mediated C–C coupling. In contrast, elevated pressures (≥ 7.0 MPa) suppress hydrocarbon formation and promotes the production of long-chain oxygenates, including higher alcohols and carboxylic acids. Comprehensive structural characterization indicates a clear pressure-dependent phase transformation: Fe5C2 progressively diminishes and evolves into FeCO3, accompanied by increased Fe–O and carbonate surface species. Operando diffuse reflectance infrared Fourier transform spectroscopy reveals that FeCO3-rich surfaces stabilize COO-containing intermediates and inhibit C–O bond scission, favoring direct COO insertion rather than Fischer-Tropsch chain growth. CO-temperature programmed surface reaction further confirms that FeCO3 is catalytically inert toward CO activation, explaining the reduced CO2 conversion observed at high pressure. The combined results establish FeCO3 as a pressure-generated phase that redirects CO2 hydrogenation from hydrocarbon-selective to oxygenate-selective pathways. This work provides mechanistic insight into pressure-driven catalyst restructuring and offers a new strategy for tuning oxygenate selectivity in CO2 hydrogenation.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"87 ","pages":"Pages 70-86"},"PeriodicalIF":17.2,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652097","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

Structural origins of selectivity in guaiacol hydrodeoxygenation on copper 愈创木酚对铜加氢脱氧选择性的结构来源

IF 17.2 1区化学

Chinese Journal of Catalysis Pub Date : 2026-08-01 Epub Date: 2026-08-02 DOI: 10.1016/S1872-2067(26)65098-X

Tianchun Li, Tianyang Liu, Yu Jing

{"title":"Structural origins of selectivity in guaiacol hydrodeoxygenation on copper","authors":"Tianchun Li, Tianyang Liu, Yu Jing","doi":"10.1016/S1872-2067(26)65098-X","DOIUrl":"10.1016/S1872-2067(26)65098-X","url":null,"abstract":"<div><div>Efficient upgrading of lignin-derived bio-oils requires selective hydrodeoxygenation (HDO) of oxygen-containing groups without hydrogenating the aromatic ring, a central challenge in biomass valorization. Here we combine density functional theory and microkinetic simulations to elucidate the HDO mechanism of guaiacol on copper catalysts. Across Cu(100), Cu(111), and Cu(211) surfaces, two competing routes dominate product distribution: (1) hydrogen-assisted deoxygenation (H-DO) via methoxy dissociation, producing phenol, and (2) partial hydrogenation (PHDO) of the aromatic ring, leading to cyclohexanone-type products. We show that H-DO activity is largely insensitive to surface orientation due to weak Cu-C2 interactions, whereas PHDO activity depends strongly on surface structure through Cu-C3/C6 bonding. This difference establishes the d-band center as a reliable electronic descriptor for selectivity. Cu(111), with its more negative d-band center and weaker adsorption, exhibits the highest aromatic selectivity. Guided by this insight, we propose and validate grain boundary (GB) engineering as a design strategy: Cu(111)/(111) GB selectively suppresses PHDO by destabilizing hydrogenation transition states, while retaining H-DO activity. These results establish a clear structure-activity-selectivity relationship for guaiacol HDO and demonstrate that electronic tuning through facet and GB control provides a general framework for designing metal catalysts for selective biomass upgrading.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"87 ","pages":"Pages 376-385"},"PeriodicalIF":17.2,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148652132","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