Methanol conversion on borocarbonitride catalysts: Identification and quantification of active sites
Methanol conversion on borocarbonitride catalysts: Identification and quantification of active sites
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硼碳氮化物催化剂上的甲醇转化：活性位点的识别和定量
DOI：
10.1126/sciadv.aba5778
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发表时间：
2020-06
期刊：
影响因子：
13.6
通讯作者：
Xie Zailai
中科院分区：
文献类型：
--
作者：
Zhang Xuefei;Yan Pengqiang;Xu Junkang;Li Fan;Herold Felix;Etzold Bastian J. M.;Wang Peng;Su Dang Sheng;Lin Sen;Qi Wei;Xie Zailai
通过活性中心定量和动力学分析揭示了硼碳氮化物上甲醇转化的本质。硼碳氮化物（BCN）已成为氧化脱氢（ODH）反应的高选择性催化剂。然而，由于BCN催化剂表面含氧官能团的复杂性，对BCN催化剂的催化机理还缺乏深入的了解。在这里，BCN纳米管与多个活性中心的合成用于氧辅助甲醇转化反应。该催化剂对甲醇的转化率（29%）和甲醛的选择性（54%）有显著的提高。动力学研究表明，BCN上的羧酸基团对二甲醚的生成起催化作用，而酮羰基和硼羟基（B─OH）对甲醛的生成起氧化还原催化作用。原位红外光谱、X射线吸收光谱和密度泛函理论进一步揭示了B─OH位上的ODH反应途径。本工作为BCN催化剂的功能机理提供了物理化学的见解，为进一步开发研究不足的非金属催化体系铺平了道路。
The nature of methanol conversion on borocarbonitride was revealed via active site quantification and kinetic analysis. Borocarbonitrides (BCNs) have emerged as highly selective catalysts for the oxidative dehydrogenation (ODH) reaction. However, there is a lack of in-depth understanding of the catalytic mechanism over BCN catalysts due to the complexity of the surface oxygen functional groups. Here, BCN nanotubes with multiple active sites are synthesized for oxygen-assisted methanol conversion reaction. The catalyst shows a notable activity improvement for methanol conversion (29%) with excellent selectivity to formaldehyde (54%). Kinetic measurements indicate that carboxylic acid groups on BCN are responsible for the formation of dimethyl ether, while the redox catalysis to formaldehyde occurs on both ketonic carbonyl and boron hydroxyl (B─OH) sites. The ODH reaction pathway on the B─OH site is further revealed by in situ infrared, x-ray absorption spectra, and density functional theory. The present work provides physical-chemical insights into the functional mechanism of BCN catalysts, paving the way for further development of the underexplored nonmetallic catalytic systems.
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影响因子：
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作者：
Jian Zhang;Dangsheng Su;A. Zhang;Di Wang;R. Schlögl;C. Hébert
通讯作者：
Jian Zhang;Dangsheng Su;A. Zhang;Di Wang;R. Schlögl;C. Hébert
影响因子：
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影响因子：
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作者：
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通讯作者：
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作者：
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通讯作者：
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