Page 140 - 《精细化工》2022年第7期

第 39 卷第 7 期 精 细 化 工 Vol.39, No.7
2022 年 7 月 FINE CHEMICALS July 2022

催化与分离提纯技术
限域单原子催化剂制备及其催化湿式氧化性能

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张立涛 ，安路阳 ，尹健博 ，裴 振 ，靳承煜 ，卫皇曌
（1. 中钢集团鞍山热能研究院有限公司，辽宁省钢铁行业废水深度处理技术工程研究中心，辽宁 鞍山
114044；2. 中科院大连化学物理研究所，辽宁 大连 116023）
摘要：采用原位合成法将 Ni 单原子限域的 Ni-N 掺杂碳纳米管（NCNT）结构架构建到活性炭（AC）表面制备
了 Ni-NCNT/AC 载体，再利用浸渍法制备了负载金属 Ru 催化剂（Ru@Ni-NCNT/AC），然后评价了其在催化湿
式氧化乙酸过程中总有机碳的去除率。通过 SEM、TEM、X 射线吸收精细结构光谱（XAFS）、XPS、H 2 -TPR
和一氧化碳-漫反射傅里叶变换红外光谱（CO-DRIFTS）对样品的形貌、结构、元素价态、表面吸附和化学性质
进行了表征和分析。此外，采用密度泛函理论计算了 O 2 和乙酸分子在催化剂表面的吸附构型及吸附能。结果表
明，Ni 单原子作为催化助剂能通过改变基底材料的电子特性促进表面贵金属发挥更高的催化氧化乙酸的活性。
在温度 250 ℃、压力 6.5 MPa 条件下，连续运行 240 h，乙酸的去除率持续稳定在 95%以上，催化剂具有较高
活性和良好的稳定性。
关键词：碳纳米管；限域单原子；湿式氧化；助剂；催化技术
中图分类号：X703；TQ426 文献标识码：A 文章编号：1003-5214 (2022) 07-1426-08

Preparation and wet oxidation properties of domain-confined
single-atomic catalyst

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ZHANG Litao , AN Luyang , YIN Jianbo , PEI Zhen , JIN Chengyu , WEI Huangzhao
（1. Engineering Research Center of Iron and Steel Industry Wastewater Advanced Treatment Technology of Liaoning
Province, Sinosteel Anshan Research Institute of Thermo-Energy Co., Ltd., Anshan 114044, Liaoning, China; 2. Dalian
Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China）
Abstract: Ni-NCNT/AC carrier was firstly synthesized by in-situ growth of single atom Ni confined Ni-N
doped carbon nanotubes (NCNT) on activated carbon (AC) surface, and then was impregnated with Ru to
prepare catalyst Ru@Ni-NCNT/AC, whose catalytic activity in wet oxidation of acetic acid was
evaluated by measuring the removal rate of total organic carbon. The morphology, structure, element
valence, surface adsorption and chemical properties of the catalyst samples were characterized and
analyzed respectively by SEM, TEM, X ray absorption fine structure spectroscopy (XAFS), XPS,
H 2-TPR and carbon monoxide diffuse reflectance infrared Fourier transform spectroscopy (CO-DRIFTS).
Moreover, the adsorption configurations as well as energies of O 2 and acetic acid on catalyst surface were
computed by density functional theory. The results showed that single atom Ni was promoter, by changing
the electronic properties of the substrate material to increase the catalytic performance of surface precious
metals for the oxidation of acetic acid. After continuous operation for 240 h at 250 ℃ and 6.5 MPa , the
removal rate of acetic acid remained stable above 95% while the catalyst retained high activity and good
stability.
Key words: carbon nanotubes; confined single-atom; wet oxidation; promoter; catalytic technology

收稿日期：2021-11-19; 定用日期：2022-03-23; DOI: 10.13550/j.jxhg.20211183
基金项目：辽宁省自然科学基金（2019-ZD-0894）
作者简介：张立涛（1989—），男，硕士，工程师，E-mail：15040786507@163.com。联系人：安路阳（1985—），男，高级工程师，
E-mail：anluyang2008@126.com。