ZnO晶面对纳米Au催化CO氧化性能的影响

doi:10.16085/j.issn.1000-6613.2020-1410

化工进展 ›› 2021, Vol. 40 ›› Issue (6): 3197-3202.DOI: 10.16085/j.issn.1000-6613.2020-1410

ZnO晶面对纳米Au催化CO氧化性能的影响

李炳鑫¹(), 周慧然¹(), 吕温馨¹, 赵晓华¹, 王晓兵¹, 张明², 娄向东¹()

^1.河南师范大学化学化工学院，河南新乡 453007
^2.洛阳金达石化有限责任公司，河南洛阳 471000

收稿日期:2020-07-21 修回日期:2020-12-21 出版日期:2021-06-06 发布日期:2021-06-22
通讯作者: 周慧然,娄向东
作者简介:李炳鑫（1995—），男，硕士，研究方向为工业催化。E-mail：abing005@126.com。
基金资助:
河南省高等学校重点科研项目应用研究计划(18A53003);河南省博士后科研项目(2017SBH003)

Crystal plane effect of ZnO on the catalytic properties of Au nanostructure for CO oxidation

LI Bingxin¹(), ZHOU Huiran¹(), LYU Wenxin¹, ZHAO Xiaohua¹, WANG Xiaobing¹, ZHANG Ming², LOU Xiangdong¹()

^1.School of Chemistry and Chemical Engineering, Henan Normal University, Xinxiang 453007, Henan, China
^2.Luoyang Jinda Petrochemistry Industry Company Limited, Luoyang 471000, Henan, China

Received:2020-07-21 Revised:2020-12-21 Online:2021-06-06 Published:2021-06-22
Contact: ZHOU Huiran,LOU Xiangdong

摘要/Abstract

摘要：

采用水热合成法制备了无择优暴露晶面的盘状ZnO（ZnO-D）和优先暴露（100）非极性面的片花状ZnO（ZnO-F）；通过沉积-沉淀法将Au纳米颗粒负载于所制备的ZnO载体表面；采用ICP、XRD、SEM、TEM、XPS和BET对合成的催化剂进行表征；最后，以CO氧化为探针反应研究载体晶面对金纳米颗粒催化性能的影响。结果表明，ZnO形貌对Au颗粒粒径影响甚微，但Au物种的电子价态表现出显著的载体形貌依赖性。以盘状和片花状ZnO为载体所获得的金催化剂的Au^δ⁺物种的原子分数分别为34.8%和67.4%，说明Au颗粒与片花状ZnO间具有更强的金属-载体相互作用。Au/ZnO-F催化剂的CO氧化活性明显优于Au/ZnO-D，归因于Au/ZnO-F具有较高的O₂吸附活化能力。本文通过调控载体形貌/晶面进而调变金属-载体间相互作用及Au物种的化学态的方法提高了Au催化性能。

关键词: 金纳米颗粒, 催化剂载体, 晶面效应, 一氧化碳, 氧化

Abstract:

To investigate the crystal plane effect of the support on the catalytic performance of Au nanoparticles, we synthesized two ZnO nanomaterials with different morphologies by a hydrothermal method, i.e. disc-like ZnO (ZnO-D) without any dominant facets and nanosheet-assembled flower-like ZnO (ZnO-F) exposing preferentially (100) nonpolar planes. Then, two different Au/ZnO catalysts were obtained via deposition-precipitation method with the as-prepared ZnO as support, characterized by ICP, XRD, SEM, TEM, XPS and BET, and evaluated with the CO oxidation reaction. The characterization results demonstrated that the Au nanoparticles deposited on ZnO with different shapes showed similar average size but different redox states. The percentage of Au^δ⁺ species in Au/ZnO-D and Au/ZnO-F were 34.8% and 67.4%, respectively, indicating stronger interaction between Au species and the flower-like ZnO. The Au/ZnO-F catalyst exhibited much higher activity than Au/ZnO-D, because of its excellent capability in adsorption and activation of O₂ molecular. This finding shows that the catalytic performance of Au-based catalysts can be enhanced by altering the interaction between Au and the support with specific crystal facets.

Key words: gold(Au) nanoparticle, catalyst support, crystal plane effect, carbon monoxide, oxidation

中图分类号:

O643

李炳鑫, 周慧然, 吕温馨, 赵晓华, 王晓兵, 张明, 娄向东. ZnO晶面对纳米Au催化CO氧化性能的影响[J]. 化工进展, 2021, 40(6): 3197-3202.

LI Bingxin, ZHOU Huiran, LYU Wenxin, ZHAO Xiaohua, WANG Xiaobing, ZHANG Ming, LOU Xiangdong. Crystal plane effect of ZnO on the catalytic properties of Au nanostructure for CO oxidation[J]. Chemical Industry and Engineering Progress, 2021, 40(6): 3197-3202.

图/表 8

图1 ZnO及Au/ZnO样品的XRD图

图2 Au/ZnO-F和Au/ZnO-D催化剂的SEM图

图3 Au/ZnO-F和Au/ZnO-D催化剂的TEM图及相应的粒径分布图

图4 Au/ZnO-F和Au/ZnO-D催化剂的Au 4f XPS图

表1 Au/ZnO-F和Au/ZnO-D催化剂中Au物种的原子分数单位：%

催化剂	Au⁰	Au⁺	Au³⁺
Au/ZnO-F	32.6	35.6	31.8
Au/ZnO-D	65.2	14.6	20.2

图5 Au/ZnO-F和Au/ZnO-D催化剂的CO氧化性能

表2 Au/ZnO-F和Au/ZnO-D的表征结果

催化剂

粒径

/nm

BET

/m²?g^?1

Au负载量/%

ICP

（质量分数）

EDS

（质量分数）

XPS

（原子分数）

图6 Au/ZnO-F和Au/ZnO-D催化剂的O2-TPD曲线

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ZnO晶面对纳米Au催化CO氧化性能的影响

Crystal plane effect of ZnO on the catalytic properties of Au nanostructure for CO oxidation

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