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学者姓名:周岩良
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Achieving green ammonia (NH3) synthesis requires developing effective catalysts under mild conditions. However, the competitive adsorption of N-2 and H-2, as well as the strong binding of N-containing intermediates on the catalyst, greatly inhibits the active sites for efficient NH3 synthesis. Here, we constructed a series of ZrH2-modified Fe catalysts with dual active sites to address these issues and realized efficient NH3 synthesis under mild conditions. Our study shows that ZrH2 can not only provide active sites for H-2 activation but also transfer electrons to Fe sites for accelerating N-2 activation. The interaction between Fe and ZrH2 over 40ZrH(2)-Fe leads to a decrease in work function and a downward shift of the d-band center, which is conducive to N-2 activation and NH3 desorption, respectively. The utilization of distinct sites for activating different reactants can avoid the competitive adsorption of N-2 and H-2, leading to excellent NH3 synthesis activity of the 40 wt.% ZrH2-mediated Fe catalyst. As a result, 40ZrH(2)-Fe exhibits a high NH3 synthesis rate of 23.3 mmol g(cat)(-1) h(-1) at 400 degrees C and 1 MPa and robust stability during 100 h time-on-stream.
Keyword :
ammonia synthesis ammonia synthesis competitive adsorption competitive adsorption dual-site catalyst dual-site catalyst N-2 activation N-2 activation synergistic effect synergistic effect
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GB/T 7714 | Zhang, Shiyong , Zhang, Mingyuan , Zhang, Tianhua et al. A dual-site Fe-based catalyst for efficient ammonia synthesis under mild conditions [J]. | SCIENCE CHINA-CHEMISTRY , 2025 , 68 (4) : 1576-1584 . |
MLA | Zhang, Shiyong et al. "A dual-site Fe-based catalyst for efficient ammonia synthesis under mild conditions" . | SCIENCE CHINA-CHEMISTRY 68 . 4 (2025) : 1576-1584 . |
APA | Zhang, Shiyong , Zhang, Mingyuan , Zhang, Tianhua , Sun, Jizhen , Li, Jiaxin , Su, Kailin et al. A dual-site Fe-based catalyst for efficient ammonia synthesis under mild conditions . | SCIENCE CHINA-CHEMISTRY , 2025 , 68 (4) , 1576-1584 . |
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To date, NH3 synthesis under mild conditions is largely confined to precious Ru catalysts, while nonprecious metal (NPM) catalysts are confronted with the challenge of low catalytic activity due to the inverse relationship between the N-2 dissociation barrier and NHx (x = 1-3) desorption energy. Herein, we demonstrate NPM (Co, Ni, and Re)-mediated Mo2CTx MXene (where T-x denotes the OH group) to achieve efficient NH3 synthesis under mild conditions. In particular, the NH3 synthesis rate over Re/Mo2CTx and Ni/Mo2CTx can reach 22.4 and 21.5 mmol g(-1) h(-1) at 400 degrees C and 1 MPa, respectively, higher than that of NPM-based catalysts and Cs-Ru/MgO ever reported. Experimental and theoretical studies reveal that Mo4+ over Mo2CTx has a strong ability for N-2 activation; thus, the rate-determining step is shifted from conventional N-2 dissociation to NH2* formation. NPM is mainly responsible for H-2 activation, and the high reactivity of spillover hydrogen and electron transfer from NPM to the N-rich Mo2CTx surface can efficiently facilitate nitrogen hydrogenation and the subsequent desorption of NH3. With the synergistic effect of the dual active sites bridged by H-spillover, the NPM-mediated Mo2CTx catalysts circumvent the major obstacle, making NH3 synthesis under mild conditions efficient.
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GB/T 7714 | Zhou, Yanliang , Liang, Lili , Wang, Congying et al. Precious-Metal-Free Mo-MXene Catalyst Enabling Facile Ammonia Synthesis Via Dual Sites Bridged by H-Spillover [J]. | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY , 2024 , 146 (33) : 23054-23066 . |
MLA | Zhou, Yanliang et al. "Precious-Metal-Free Mo-MXene Catalyst Enabling Facile Ammonia Synthesis Via Dual Sites Bridged by H-Spillover" . | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146 . 33 (2024) : 23054-23066 . |
APA | Zhou, Yanliang , Liang, Lili , Wang, Congying , Sun, Fuxiang , Zheng, Lirong , Qi, Haifeng et al. Precious-Metal-Free Mo-MXene Catalyst Enabling Facile Ammonia Synthesis Via Dual Sites Bridged by H-Spillover . | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY , 2024 , 146 (33) , 23054-23066 . |
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Olefins are important building blocks that have been extensively used to produce diverse consumer products in petrochemical industry. Owing to the requirement of low-carbon-footprint processes and the increasing use of light alkanes sourced from shale gas, an environmentally friendly and economic route alternative to the state-of-the-art steam cracking of crude oil has been investigated for olefin production. The oxidative dehydrogenation (ODH) of alkanes to olefins has attracted wide attention due to the absence of thermodynamic limitations and coke formation. However, excessive oxidation of olefin is prone to occur in this process. Developing a suitable ODH catalyst with high performance, particularly with enhanced selectivity, is more and more urgent but still remains a challenge. In this Review, we talk about the representative currently developed isolation strategies to optimize the selectivity of olefins via the ODH process, particularly for the conversion of ethane to ethylene, which include the dispersion regulation of metal oxide, the isolation of metal and nonmetal sites, the construction of dual functional sites to isolate dehydrogenation and oxidation steps, and the adoption of selective oxygen species with the promotion of soft oxidants as reactants. Furthermore, the mechanistic aspects about the activation of ethane and the participation of oxygen species for tailoring the selectivity are then classified and discussed in detail. Finally, the perspectives and the emerging technologies for the ODH process are listed and evaluated.
Keyword :
active site active site olefins olefins oxidative dehydrogenation oxidative dehydrogenation oxygen species oxygen species selectivity selectivity
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GB/T 7714 | Chai, Yicong , Zhou, Yanliang , Lin, Sen et al. Tailoring the Olefin Selectivity in Catalytic Oxidative Dehydrogenation of Light Alkane by the Isolation Strategy [J]. | ACS CATALYSIS , 2024 , 14 (4) : 2502-2521 . |
MLA | Chai, Yicong et al. "Tailoring the Olefin Selectivity in Catalytic Oxidative Dehydrogenation of Light Alkane by the Isolation Strategy" . | ACS CATALYSIS 14 . 4 (2024) : 2502-2521 . |
APA | Chai, Yicong , Zhou, Yanliang , Lin, Sen , Wang, Xiaodong , Lin, Jian . Tailoring the Olefin Selectivity in Catalytic Oxidative Dehydrogenation of Light Alkane by the Isolation Strategy . | ACS CATALYSIS , 2024 , 14 (4) , 2502-2521 . |
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The effects of promoters on Ru nanoparticles (>= 2 nm) catalysts for NH3 synthesis have been extensively elaborated, but their roles on ultrasmall Ru nanoclusters (NCs, 1-2 nm) remain largely unknown and need to be further uncovered. Herein, a series of K-promoted MgO supported Ru NCs were synthesized and investigated for NH3 synthesis. The addition of 5wt.%K onto Ru/MgO NCs leads to a significantly high NH3 synthesis rate of 21.7 mmol(NH3) g(cat)(-1)h(-1) at 400 degrees C and 0.2 MPa, close to the thermodynamic equilibrium. Out studies reveal that anchoring K onto Ru NCs can increase the electron density and cause an upshift of the d-band center of Ru entities. Moreover, the addition of K regulates the hydrogen affinity and accelerates the migration of hydrogen from the Ru NCs surface to MgO support, which is crucial in avoiding the hydrogen poisoning effect on Ru NCs. With the synergistic effect of the Ru NCs sites bridged by H-spillover, makes the K-mediated Ru/MgO NCs catalysts efficient for NH3 synthesis at mild conditions.
Keyword :
Ammonia synthesis Ammonia synthesis Electronic structure Electronic structure Hydrogen spillover Hydrogen spillover Oxygen vacancies Oxygen vacancies Ultrasmall Ru nanoclusters Ultrasmall Ru nanoclusters
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GB/T 7714 | Peng, Xuanbei , Luo, Yongjin , Zhang, Tianhua et al. Potassium promoter regulates electronic structure and hydrogen spillover of ultrasmall Ru nanoclusters catalyst for ammonia synthesis [J]. | CHEMICAL ENGINEERING SCIENCE , 2024 , 292 . |
MLA | Peng, Xuanbei et al. "Potassium promoter regulates electronic structure and hydrogen spillover of ultrasmall Ru nanoclusters catalyst for ammonia synthesis" . | CHEMICAL ENGINEERING SCIENCE 292 (2024) . |
APA | Peng, Xuanbei , Luo, Yongjin , Zhang, Tianhua , Deng, Jinxiu , Zhou, Yanliang , Li, Jiaxin et al. Potassium promoter regulates electronic structure and hydrogen spillover of ultrasmall Ru nanoclusters catalyst for ammonia synthesis . | CHEMICAL ENGINEERING SCIENCE , 2024 , 292 . |
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Ammonia (NH3) is closely related to the fields of food and energy that humans depend on. The exploitation of advanced catalysts for NH3 synthesis has been a research hotspot for more than one hundred years. Previous studies have shown that the Ru B5 sites (step sites on the Ru (0001) surface uniquely arranged with five Ru atoms) and Fe C7 sites (iron atoms with seven nearest neighbors) over nanoparticle catalysts are highly reactive for N2-to-NH3 conversion. In recent years, single-atom and cluster catalysts, where the B5 sites and C7 sites are absent, have emerged as promising catalysts for efficient NH3 synthesis. In this review, we focus on the recent advances in single-atom and cluster catalysts, including single-atom catalysts (SACs), single-cluster catalysts (SCCs), and bimetallic-cluster catalysts (BCCs), for thermocatalytic NH3 synthesis at mild conditions. In addition, we discussed and summarized the unique structural properties and reaction performance as well as reaction mechanisms over single-atom and cluster catalysts in comparison with traditional nanoparticle catalysts. Finally, the challenges and prospects in the rational design of efficient single-atom and cluster catalysts for NH3 synthesis were provided. Recent advances in single-atom and cluster catalysts, including single-atom catalysts (SACs), single-cluster catalysts (SCCs), and bimetallic-cluster catalysts (BCCs), for thermocatalytic NH3 synthesis at mild conditions.
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GB/T 7714 | Peng, Xuanbei , Zhang, Mingyuan , Zhang, Tianhua et al. Single-atom and cluster catalysts for thermocatalytic ammonia synthesis at mild conditions [J]. | CHEMICAL SCIENCE , 2024 , 15 (16) : 5897-5915 . |
MLA | Peng, Xuanbei et al. "Single-atom and cluster catalysts for thermocatalytic ammonia synthesis at mild conditions" . | CHEMICAL SCIENCE 15 . 16 (2024) : 5897-5915 . |
APA | Peng, Xuanbei , Zhang, Mingyuan , Zhang, Tianhua , Zhou, Yanliang , Ni, Jun , Wang, Xiuyun et al. Single-atom and cluster catalysts for thermocatalytic ammonia synthesis at mild conditions . | CHEMICAL SCIENCE , 2024 , 15 (16) , 5897-5915 . |
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氨是重要的化肥原料,也是颇具潜力的氢能源载体,对于可再生能源的储存、运输和终端利用至关重要.然而,传统Haber-Bosch工艺合成氨的反应条件苛刻,需要高温高压条件,并消耗大量化石能源及排放大量二氧化碳.可再生能源电解水制氢耦合温和合成氨新技术(eHB),不仅能实现可再生能源电力的"消纳和调峰",而且可进行低成本、跨地域长距离存储运输,并可将"绿氨"与氢能产业相结合.然而,现有的高温高压合成氨催化剂与eHB工艺相不匹配,因此,迫切需要开发温和条件下高效合成氨催化剂技术,以实现可再生能源电力电解制氢体系和合成氨技术互补融合.目前,虽然助剂对于Ru基纳米簇(≥l nm)合成氨催化剂的影响规律已得到了广泛研究,但它们对于Ru原子簇催化剂的作用机制尚不清楚,需要进一步揭示. 本文考察了Ba及Ce助剂对Ru原子簇催化剂的影响规律,并分析了其作用机制.首先,通过简单的浸渍法将Ba和/或Ce物种掺杂到Ru原子簇催化剂(2 wt%Ru ACCs),制得Ba/Ce/2 wt%Ru ACCs催化剂;然后,通过一系列实验考察了这些催化剂的合成氨性能,并利用多种表征手段对其进行了深入分析.合成氨性能测试结果表明,添加Ba和Ce助剂后,2 wt%Ru ACCs催化剂的合成氨速率明显提高,在400℃和1 MPa下,Ba/Ce/2 wt%Ru ACCs催化剂的合成氨反应速率达到56.2 mmolNH3 gcat-1 h1,是2 wt%Ru ACCs的7.5倍,且催化剂表现出较好的稳定性,在稳定运行140 h后活性未见明显降低.球差校正电子显微镜和X射线吸收精细结构谱结果表明,负载Ba和/或Ce后,Ru以Ru3原子簇形式存在.X射线吸收近边结构谱和X射线光电子能谱结果表明,Ru与Ba及Ce物种之间存在较强的簇-金属氧化物助剂电子相互作用,可促进电子转移到Ru物种,形成富电子状态的Ru,进而促使电子转移到N2的π*反键轨道,提高温和条件下合成氨反应速率.利用25%N2+75%D2气氛下的原位红外光谱研究催化剂的合成氨反应机理,结果表明,在Ba/Ce/2 wt%Ru ACCs催化剂表面同时检测到N2D2物种和N2Dx物种的振动吸收峰,说明添加Ba和/或Ce物种没有改变Ru原子簇催化剂活化N2的方式,N2仍是通过加氢的路径合成氨. 综上,本文考察了助剂对Ru原子簇的影响规律,揭示了其作用机制,为设计高效的温和条件合成氨催化剂提供参考.
Keyword :
N2活化 N2活化 助剂 助剂 原子簇 原子簇 合成氨 合成氨 电子相互作用 电子相互作用
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GB/T 7714 | 张天华 , 胡海慧 , 李嘉欣 et al. 簇-金属氧化物助剂电子相互作用调控的Ru原子簇催化剂用于温和条件下合成氨反应 [J]. | 催化学报 , 2024 , 60 (5) : 209-218 . |
MLA | 张天华 et al. "簇-金属氧化物助剂电子相互作用调控的Ru原子簇催化剂用于温和条件下合成氨反应" . | 催化学报 60 . 5 (2024) : 209-218 . |
APA | 张天华 , 胡海慧 , 李嘉欣 , 高迎龙 , 李玲玲 , 张明远 et al. 簇-金属氧化物助剂电子相互作用调控的Ru原子簇催化剂用于温和条件下合成氨反应 . | 催化学报 , 2024 , 60 (5) , 209-218 . |
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Promoting the thermal stability of supported noble metal catalysts under harsh conditions remains challenging for the modern chemistry industry. Herein, Fe-substituted hexaaluminate supported Pt catalysts (Pt/BaFeAl11O19) were synthesized and treated with high temperature at 800 degrees C under different atmospheres. The Pt particles showed severe sintering under an oxidative atmosphere but high stability under reductive conditions. Interestingly, Pt/BaFeAl11O19 pre-reduced at high temperature possessed improved anti-sintering ablility during oxidative annealing. The characterization results demonstrate that oxygen vacancies were facilely formed under an H-2 atmosphere to favor the formation of coating layers on Pt nanoparticles. This structure helps retain oxygen vacancies during subsequent oxidative calcination, contributing to promoted stability. The high thermal stability of Pt particles coupled with the easy generation of Fe2+ sites in Pt/BaFeAl11O19 resulted in excellent catalytic performance for CO and C3H8 oxidation after cycling hydrothermal aging at 800 degrees C.
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GB/T 7714 | Xu, Yumeng , Chen, Rongzhou , Tang, Hailian et al. High temperature reductive treatment promotes thermal stability of Pt/hexaaluminate catalysts for CO and C3H8 oxidation [J]. | CATALYSIS SCIENCE & TECHNOLOGY , 2024 , 14 (20) : 6065-6075 . |
MLA | Xu, Yumeng et al. "High temperature reductive treatment promotes thermal stability of Pt/hexaaluminate catalysts for CO and C3H8 oxidation" . | CATALYSIS SCIENCE & TECHNOLOGY 14 . 20 (2024) : 6065-6075 . |
APA | Xu, Yumeng , Chen, Rongzhou , Tang, Hailian , Yan, Lu , Huang, Fei , Tian, Ming et al. High temperature reductive treatment promotes thermal stability of Pt/hexaaluminate catalysts for CO and C3H8 oxidation . | CATALYSIS SCIENCE & TECHNOLOGY , 2024 , 14 (20) , 6065-6075 . |
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Ammonia (NH3) plays an important role in the development and evolution of Earth's life system. The extremely high bond energy (941 kJ mol(-1)) of N-2 hinder the conversion of N-2 to NH3 under mild conditions. Meanwhile, clearly identifying the distribution of intermediates for NH3 synthesis remains a huge challenge in the experiment. Herein, we anchored carbon clusters (C-60 or C-70) onto Ru catalysts supported on rare earth oxides, forming a class of Ru-carbon cluster co-catalysts that exhibit strong electronic metal-carbon cluster interaction (EMCI). Carbon clusters function as an electron buffer that induced electron uptake from metallic Ru sites and concurrently provides electron feedback to Ru delta+ in a reversible manner, achieving a flexible balance of electron density at the Ru active sites. Moreover, H-affinitive carbon clusters serve as the site for the adsorption, activation and migration of hydrogen. With Ru and carbon clusters synergistically bridged by hydrogen spillover, the Ru-C-60 co-catalyst exhibits an exceptionally high NH3 synthesis rate and remarkable stability. Experimental provides direct evidence of the distribution and evolution of *N2Hx (x = 1 similar to 3) intermediates, with the hydrogenation of *NH2 to form *NH3 identified as the rate-determining step. This work paves the way for utilizing carbon clusters in important chemical reactions.
Keyword :
ammonia synthesis ammonia synthesis carbon clusters carbon clusters electron buffer electron buffer N-2 activation N-2 activation reaction mechanism reaction mechanism
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GB/T 7714 | Zhang, Mingyuan , Luo, Yongjin , Peng, Xuanbei et al. Contribution of Carbon Clusters to Ammonia Synthesis Over Ru-Based Catalysts [J]. | ADVANCED FUNCTIONAL MATERIALS , 2024 , 35 (8) . |
MLA | Zhang, Mingyuan et al. "Contribution of Carbon Clusters to Ammonia Synthesis Over Ru-Based Catalysts" . | ADVANCED FUNCTIONAL MATERIALS 35 . 8 (2024) . |
APA | Zhang, Mingyuan , Luo, Yongjin , Peng, Xuanbei , Zhang, Shiyong , Zhang, Lei , Xu, Cong-Qiao et al. Contribution of Carbon Clusters to Ammonia Synthesis Over Ru-Based Catalysts . | ADVANCED FUNCTIONAL MATERIALS , 2024 , 35 (8) . |
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Pretreatment under specific atmosphere is a general strategy to activate catalysts. How physicochemical properties of supports are modulated during activation process and their influence on active sites are still the ongoing topic. Herein, the effect of reaction gas treatment on performance of phosphorus modified Pd/Al2O3 catalysts in lean methane oxidation was studied. The pretreated Pd/P-doped Al2O3 catalyst exhibited a full conversion of CH4 at similar to 400 degrees C, excellent stability under both dry and wet conditions. Characterization results reveal that the uniform and stable P species in Al2O3 enhanced the metal-support interaction and availability of oxygen in support. Under reaction gas condition, PdO-support connection was further promoted to favor generation of oxygen vacancies on support with the help of CH4, leading to weakened Pd-O bond, facile reformation and increased fraction of PdO. These facilitated formation of intermediates and surface dehydroxylation and mitigated the deactivation caused by thermodynamic decomposition of PdO. (c) 2023 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Keyword :
Alumina Alumina Lean CH4 oxidation Lean CH4 oxidation Metal-support interaction Metal-support interaction Pd Pd Phosphorus Phosphorus
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GB/T 7714 | Yan, Lu , Chen, Rongzhou , Wei, Haisheng et al. Reaction gas treatment promoting activity and stability of PdO for lean methane oxidation over phosphorus modified Pd/Al2O3 catalysts [J]. | INTERNATIONAL JOURNAL OF HYDROGEN ENERGY , 2023 , 48 (61) : 23516-23529 . |
MLA | Yan, Lu et al. "Reaction gas treatment promoting activity and stability of PdO for lean methane oxidation over phosphorus modified Pd/Al2O3 catalysts" . | INTERNATIONAL JOURNAL OF HYDROGEN ENERGY 48 . 61 (2023) : 23516-23529 . |
APA | Yan, Lu , Chen, Rongzhou , Wei, Haisheng , Zhou, Yanliang , Hong, Bilv , Yang, Yijia et al. Reaction gas treatment promoting activity and stability of PdO for lean methane oxidation over phosphorus modified Pd/Al2O3 catalysts . | INTERNATIONAL JOURNAL OF HYDROGEN ENERGY , 2023 , 48 (61) , 23516-23529 . |
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Direct selective oxidation of methane (DSOM) to highvalue-addedoxygenates under mild conditions is attracting considerable interest.Although state-of-the-art supported metal catalysts can improve methaneconversion, it is still challenging to avoid the deep oxidation ofoxygenates. Here, we develop a highly efficient metal-organicframeworks (MOFs)-supported single-atom Ru catalyst (Ru-1/UiO-66) for the DSOM reaction using H2O2 asan oxidant. It endows nearly 100% selectivity and an excellent turnoverfrequency of 185.4 h(-1) for the production of oxygenates.The yield of oxygenates is an order of magnitude higher than thaton UiO-66 alone and several times higher than that on supported Runanoparticles or other conventional Ru-1 catalysts, whichshow severe CO2 formation. Detailed characterizations anddensity functional theory calculations reveal a synergistic effectbetween the electron-deficient Ru-1 site and the electron-richZr-oxo nodes of UiO-66 on Ru-1/UiO-66. The Ru-1 site is responsible for the activation of CH4 via theresulting Ru-1=O* species, while the Zr-oxo nodesundertake the formation of oxygenic radical species to produce oxygenates.In particular, the Zr-oxo nodes retrofitted by Ru-1 canprune the excess H2O2 to inactive O-2 more than (OH)-O-center dot species, helping to suppress theover-oxidation of oxygenates.
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GB/T 7714 | Fang, Geqian , Wei, Fenfei , Lin, Jian et al. Retrofitting Zr-Oxo Nodes of UiO-66 by Ru Single Atoms to Boost Methane Hydroxylation with Nearly Total Selectivity [J]. | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY , 2023 , 145 (24) : 13169-13180 . |
MLA | Fang, Geqian et al. "Retrofitting Zr-Oxo Nodes of UiO-66 by Ru Single Atoms to Boost Methane Hydroxylation with Nearly Total Selectivity" . | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 145 . 24 (2023) : 13169-13180 . |
APA | Fang, Geqian , Wei, Fenfei , Lin, Jian , Zhou, Yanliang , Sun, Li , Shang, Xin et al. Retrofitting Zr-Oxo Nodes of UiO-66 by Ru Single Atoms to Boost Methane Hydroxylation with Nearly Total Selectivity . | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY , 2023 , 145 (24) , 13169-13180 . |
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