以RuCl<sub>3</sub>/SiO<sub>2</sub>为模板制备高性能镶嵌式钌基氨合成催化剂

引用本文: 周亚萍, 马永承, 蓝国钧, 唐浩东, 韩文锋, 刘化章, 李瑛. 以RuCl₃/SiO₂为模板制备高性能镶嵌式钌基氨合成催化剂[J]. 催化学报, 2019, 40(1): 114-123. doi: 10.1016/S1872-2067(18)63192-4 shu

Citation: Yaping Zhou, Yongcheng Ma, Guojun Lan, Haodong Tang, Wenfeng Han, Huazhang Liu, Ying Li. A highly stable and active mesoporous ruthenium catalyst for ammonia synthesis prepared by a RuCl₃/SiO₂-templated approach[J]. Chinese Journal of Catalysis, 2019, 40(1): 114-123. doi: 10.1016/S1872-2067(18)63192-4 shu

以RuCl₃/SiO₂为模板制备高性能镶嵌式钌基氨合成催化剂

a 浙江工业大学工业催化研究所, 浙江杭州 310014;
b 四川省华地建设工程有限责任公司, 四川成都 610081
基金项目:
国家自然科学基金（20803064）；浙江省自然科学基金（LY17B030010）.

摘要: 合成氨工业是国家能源与战略的基石，是化学工业的支柱产业，随着国家产业升级与转型，对合成氨工业的能耗提出了较为严厉的要求.钌基催化剂被誉为继铁催化剂后的第二代氨合成催化剂，与铁催化剂相比，钌基催化剂在低温和低压下具有优异的催化性能.炭材料因具有低成本、高比表面积以及电子传输和热传输等独特性能，比其它化合物如MgO，Al₂O₃和BN等更适合作为Ru催化剂的载体，而且也是除铁催化剂外唯一已工业化的载体.虽然炭负载钌催化剂的甲烷化是不可避免的，但BP公司使用石墨化碳作为载体成功地解决了这个问题，并实现了工业化.为了进一步提高钌基催化剂性能，对钌炭催化剂的结构设计尤为重要.
中孔炭（MC）孔隙结构发达，可以为钌纳米粒子的分散提供空间，从而有效提高金属钌的利用率，中孔炭负载的钌基催化剂在合成氨反应中表现出优异的催化性能.传统负载型钌基催化剂的制备一般采用浸渍法，虽然可获得高分散的Ru纳米粒子，但其只会分布在载体的表面，因此在反应过程中就容易发生金属纳米粒子的团聚和流失，大大降低使用寿命.而随着新材料制备技术的发展，对催化剂的设计合成方法的研究也越来越多.当金属纳米粒子被镶嵌在载体的壁上时，金属和载体之间就具有较强的相互作用，因而可以稳定金属纳米粒子.
本文通过蔗糖原位炭化法将Ru纳米颗粒半嵌入在炭材料中制备镶嵌式Ru-MC催化剂，并采用HRTEM，CO化学吸附等手段系统研究了镶嵌式Ru-MC催化剂与传统浸渍法制备的负载型Ru/MC催化剂之间的差异.采用等体积浸渍法添加Ba和K助剂制备催化剂Ba-K/Ru-MC和Ba-Ru-K/MC.和Ba-Ru-K/MC催化剂相比，Ba-K/Ru-MC催化剂上钌炭相互作用力增强，不但有效提高了钌催化剂的催化活性，而且提高了该催化剂的抗甲烷化能力，从而提高了氨合成条件下催化剂的稳定性和使用寿命.采用该方法制备的钌基催化剂在400℃，10000h^-1，10MPa和H₂/N₂=3.0的反应条件下，氨合成反应速率可以达到133mmol/（g·h），其性能远高于目前报导的钌基催化剂和传统的熔铁催化剂.

关键词:

English

A highly stable and active mesoporous ruthenium catalyst for ammonia synthesis prepared by a RuCl₃/SiO₂-templated approach

a Institute of Industry Catalysis, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China;
b Sichuan Huadi Construction Engineering Co., Ltd., Chengdu 610081, Sichuan, China
Received Date: 12 September 2018
Revised Date: 19 October 2018
Fund Project:
This work was supported by the National Natural Science Foundation of China (20803064), and the Natural Science Foundation of Zhejiang Provence (LY17B030010).

Abstract: Molecular nitrogen is relatively inert and the activation of its triple bond is full of challenges and of significance. Hence, searching for an efficiently heterogeneous catalyst with high stability and dispersion is one of the important targets of chemical technology. Here, we report a Ba-K/Ru-MC catalyst with Ru particle size of 1.5-2.5 nm semi-embedded in a mesoporous C matrix and with dual promoters of Ba and K that exhibits a higher activity than the supported Ba-Ru-K/MC catalyst, although both have similar metal particle sizes for ammonia synthesis. Further, the Ba-K/Ru-MC catalyst is more active than commercial fused Fe catalysts and supported Ru catalysts. Characterization techniques such as high-resolution transmission electron microscopy, N₂ physisorption, CO chemisorption, and temperature-programmed reduction suggest that the Ru nanoparticles have strong interactions with the C matrix in Ba-K/Ru-MC, which may facilitate electron transport better than supported nanoparticles.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

以RuCl₃/SiO₂为模板制备高性能镶嵌式钌基氨合成催化剂

English

A highly stable and active mesoporous ruthenium catalyst for ammonia synthesis prepared by a RuCl₃/SiO₂-templated approach

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中国化学会秘书处

以RuCl3/SiO2为模板制备高性能镶嵌式钌基氨合成催化剂

English

A highly stable and active mesoporous ruthenium catalyst for ammonia synthesis prepared by a RuCl3/SiO2-templated approach

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

以RuCl₃/SiO₂为模板制备高性能镶嵌式钌基氨合成催化剂

A highly stable and active mesoporous ruthenium catalyst for ammonia synthesis prepared by a RuCl₃/SiO₂-templated approach

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs