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[Cu_(2)O_(x)]^(2+)-ZSM-5结构及其催化甲烷氧化生成甲醇机理
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作者 边帅 左志军 +1 位作者 黄伟 阎智锋 《煤炭学报》 EI CAS CSCD 北大核心 2022年第S01期316-322,共7页
铜基分子筛催化剂是一种可在低温条件下将甲烷直接催化转化为甲醇的催化剂。为探究双核铜中心的[Cu_(2)O_(x)]^(2+)-ZSM-5(x=1,2)的结构及其催化甲烷直接氧化生成甲醇的反应机理,基于密度泛函理论,根据[Cu_(2)]^(2+)-ZSM-5在O_(2)预处... 铜基分子筛催化剂是一种可在低温条件下将甲烷直接催化转化为甲醇的催化剂。为探究双核铜中心的[Cu_(2)O_(x)]^(2+)-ZSM-5(x=1,2)的结构及其催化甲烷直接氧化生成甲醇的反应机理,基于密度泛函理论,根据[Cu_(2)]^(2+)-ZSM-5在O_(2)预处理后形成的[Cu_(2)O_(2)]^(2+)-ZSM-5结构及其稳定性差异,研究了[Cu_(2)O_(2)]^(2+)-ZSM-5→[Cu_(2)O]^(2+)-ZSM-5→[Cu_(2)]^(2+)-ZSM-5连续催化CH_(4)直接氧化生成CH_(3)OH的过程。结果表明,[Cu_(2)]^(2+)-ZSM-5更倾向于形成[(CuO)_(2)]^(2+)-ZSM-5,[CuOOCu]^(2+)-ZSM-5和[CuO_(2)Cu]^(2+)-ZSM-5三种含有O-O键的[Cu_(2)O_(2)]^(2+)-ZSM-5催化剂结构,而O-O键断裂形成的[CuOCuO]^(2+)-ZSM-5所需克服的能垒较高,且稳定性差。[(CuO)_(2)]^(2+)-ZSM-5,[CuO_(2)Cu]^(2+)-ZSM-5,[CuOOCu]^(2+)-ZSM-5和[Cu_(2)O]^(2+)-ZSM-5均可催化CH_(4)直接氧化生成CH_(3)OH。[CuO_(2)Cu]^(2+)-ZSM-5表现出最高的催化活性,催化氧化CH_(4)生成CH_(3)OH反应控速步骤为吸附态CH_(4)的解离,能垒为150.69 kJ/mol,总反应热为-131.60 kJ/mol。电子结构分析表明,当O原子具有较高的电子离域性和更靠近费米能级的p带中心时,其催化活性较高。 展开更多
关键词 [Cu_(2)O_(x)]^(2+)-ZSM-5 [Cu_(2)O]^(2+)-ZSM-5 甲烷直接氧化 甲醇 氧气 密度泛函理论
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A review of the direct oxidation of methane to methanol 被引量:7
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作者 韩宝斋 杨扬 +4 位作者 许妍妍 U.J.Etim 乔柯 许本静 阎子峰 《Chinese Journal of Catalysis》 SCIE EI CAS CSCD 北大核心 2016年第8期1206-1215,共10页
This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol (DMTM) with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by t... This article briefly reviewed the advances in the process of the direct oxidation of methane to methanol (DMTM) with both heterogeneous and homogeneous oxidation. Attention was paid to the conversion of methane by the heterogeneous oxidation process with various transition metal ox‐ides. The most widely studied catalysts are based on molybdenum and iron. For the homogeneous gas phase oxidation, several process control parameters were discussed. Reactor design has the most crucial role in determining its commercialization. Compared to the above two systems, aque‐ous homogenous oxidation is an efficient route to get a higher yield of methanol. However, the cor‐rosive medium in this method and its serious environmental pollution hinder its widespread use. The key challenge to the industrial application is to find a green medium and highly efficient cata‐lysts. 展开更多
关键词 METHANE Direct oxidation METHANOL Heterogeneous oxidation Gas-phase homogeneous oxidation Aqueous catalyzed oxidation
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