不同形貌MgAl LDH的制备及Pt/LDH的催化加氢性能

doi:10.15541/jim20210100

无机材料学报 ›› 2021, Vol. 36 ›› Issue (12): 1283-1289.DOI: 10.15541/jim20210100

所属专题：【虚拟专辑】化学反应催化剂(2020~2021)

不同形貌MgAl LDH的制备及Pt/LDH的催化加氢性能

刘雯雯¹(), 苗雨欣¹^,²(), 张轶扉¹, 王心宇¹, 兰玉婷¹, 赵震¹^,²()

1.沈阳师范大学化学化工学院, 能源与环境催化研究所, 沈阳 110034
2.中国石油大学(北京) 重质油国家重点实验室, 北京 102249

收稿日期:2021-02-18 修回日期:2021-05-13 出版日期:2021-12-20 网络出版日期:2021-05-25
通讯作者: 苗雨欣, 讲师. E-mail: yuxinmiao@synu.edu.cn;赵震, 教授. E-mail: zhaozhen@synu.edu.cn;zhenzhao@cup.edu.cn
作者简介:刘雯雯(1997-), 女, 硕士研究生. E-mail: 1753305303@qq.com
基金资助:
国家自然科学基金青年基金(21703144);中国博士后科学基金(2018M631687);辽宁省高等学校基本科研项目(LFW201705);辽宁省高等学校基本科研项目(LQN201715);沈阳师范大学博士启动项目(BS201805)

Preparation of MgAl LDH with Various Morphologies and Catalytic Hydrogenation Performance of Pt/LDH Catalysts

LIU Wenwen¹(), MIAO Yuxin¹^,²(), ZHANG Yifei¹, WANG Xinyu¹, LAN Yuting¹, ZHAO Zhen¹^,²()

1. Institute of Catalysis for Energy and Environment, College of Chemistry and Chemical Engineering, Shenyang Normal University, Shenyang 110034, China
2. State Key Laboratory of Heavy Oil Processing, China University of Petroleum Beijing, Beijing 102249, China

Received:2021-02-18 Revised:2021-05-13 Published:2021-12-20 Online:2021-05-25
Contact: MIAO Yuxin, lecturer. E-mail: yuxinmiao@synu.edu.cn;ZHAO Zhen, professor. E-mail: zhaozhen@synu.edu.cn;zhenzhao@cup.edu.cn
About author:LIU Wenwen(1997-), female, Master candidate. E-mail: 1753305303@qq.com
Supported by:
National Natural Science Foundation of China(21703144);China Postdoctoral Science Foundation(2018M631687);Basic Scientific Research Projects of Colleges and Universities of Liaoning Province(LFW201705);Basic Scientific Research Projects of Colleges and Universities of Liaoning Province(LQN201715);Doctoral Scientific Research Foundation of Shenyang Normal University(BS201805)

摘要/Abstract

摘要：

如何制备性能高效、稳定的纳米Pt催化剂, 对提高肉桂醛C=O加氢选择性具有重要的实际价值和科学意义。本研究采用共沉淀法和水热法制备不同形貌的MgAl水滑石(LDH), 用等体积浸渍法制备负载型Pt/LDH催化剂, 研究不同形貌的LDH对Pt催化肉桂醛选择加氢性能的影响。利用不同表征方法对催化剂结构、形貌、表面理化性能进行分析。结果表明, LDH载体的形貌对Pt/LDH催化剂的结构和性能影响较大, 具有片层结构的LDH纳米片与活性组分Pt之间的相互作用易于贵金属Pt的分散和稳定。同时, LDH载体中存在丰富的碱性位点和表面羟基, 有利于提高催化加氢活性和稳定性。催化性能评价表明, 在反应温度为40 ℃、反应压力为1 MPa、反应时间为120 min的条件下, 肉桂醇(CMO)的选择性为82.1%, 肉桂醛的转化率为79.8%, 经过5轮循环测试, 催化剂仍具有较好的稳定性。

关键词: MgAl水滑石, 纳米片, Pt催化剂, 肉桂醛加氢, 催化性能

Abstract:

How to design and fabricate highly efficient and stable Pt nano-catalyst is of important practical value and scientific significance for improving the C=O hydrogenation selectivity of cinnamaldehyde. In present study, a series of MgAl hydrotalcite (LDH) supports with various morphologies were synthesized by co-precipitation and hydrothermal methods. The supported Pt/LDH catalysts were prepared by incipient wet impregnation (IMP) method with LDH supports, and used for cinnamaldehyde selective hydrogenation reaction, and influences of LDH with different morphology for the catalyst activity were studied. The structure, morphology, surface physicochemical properties of these catalysts were characterized. The results show that the morphology of different supports exerts a significant influence on the structure and properties of Pt/LDH catalysts. Interaction between lamellae LDH nanosheet and active component Pt facilitates dispersing and stabilizing of Pt nanoparticles. Meanwhile, there are abundant alkaline sites and surface hydroxyl groups in the LDH support, which are beneficial to improve the catalytic hydrogenation activity and stability. Results of catalytic performance show that selectivity of cinnamon alcohol (CMO) and conversion of cinnamon aldehyde (CMA) at reaction temperature of 40 ℃, reaction pressure of 1 MPa, and reaction time of 120 min were 82.1% and 79.8%, respectively. After 5 rounds of cycle tests, the Pt/LDH catalyst still has excellent stability.

Key words: MgAl hydrotalcite, nanosheet, Pt catalyst, cinnamaldehyde hydrogenation, catalytic performance

中图分类号:

TQ174

刘雯雯, 苗雨欣, 张轶扉, 王心宇, 兰玉婷, 赵震. 不同形貌MgAl LDH的制备及Pt/LDH的催化加氢性能[J]. 无机材料学报, 2021, 36(12): 1283-1289.

LIU Wenwen, MIAO Yuxin, ZHANG Yifei, WANG Xinyu, LAN Yuting, ZHAO Zhen. Preparation of MgAl LDH with Various Morphologies and Catalytic Hydrogenation Performance of Pt/LDH Catalysts[J]. Journal of Inorganic Materials, 2021, 36(12): 1283-1289.

图/表 9

图1 不同形貌LDH的XRD图谱(a), LDH-1(b)和LDH-AS (c, d)的SEM照片, Pt/LDH-1(e)和Pt/LDH-AS(f)的TEM照片

Fig. 1 XRD patterns of different morphologies LDH (a), SEM images of LDH-1 (b) and LDH-AS (c, d), TEM images of Pt/LDH-1 (e) and Pt/LDH-AS (f)

表1 不同形貌Pt催化剂对肉桂醛加氢性能影响

Table 1 Effects of Pt catalysts with various morphologies on the hydrogenation properties of cinnamaldehyde

Catalyst	Conversion/%	Selectivity/%
Catalyst	Conversion/%	CMO	HCMA	HCMO
Pt/LDH-1	79.8	82.1	12.6	5.3
Pt/LDH-AS	42.3	89.4	8.5	2.1

表2 XPS测定Pt/LDH-1和Pt/LDH-AS催化剂的表面元素组成

Table 2 Surface elemental compositions of Pt/LDH-1 and Pt/LDH-AS catalysts determined by XPS

Catalyst	Pt content/ at%	Pt^δ⁺/Pt⁰	O_ads/(O_ads+O_lat)	Mg/Al atomic ratio
Pt/LDH-1	0.35	2.51	0.35	1.19
Pt/LDH-AS	0.28	2.30	0.21	0.98

图2 催化剂的XPS光谱

Fig. 2 XPS spectra of the as-prepared catalysts (a) Full spectrum; (b) C1s; (c) O1s; (d) Pt4f

图3 温度(a), 压力(b), 反应时间(c)和循环稳定性(d)对Pt/LDH-1催化剂的催化性能的影响

Fig. 3 Effect of temperature (a), pressure (b), reaction time (c), and recycling stability (d) on catalytic performances of Pt/LDH-1 catalysts Curves represent the conversion rate, while bar charts represent the selectivity

图S1 LDH-1和LDH-AS样品的红外光谱

Fig. S1 FT-IR spectra of LDH-1 and LDH-AS samples

图S2 所制备催化剂的CO2-TPD谱图

Fig. S2 CO2-TPD profiles of the as-prepared catalysts LDH-1 and LDH-AS supports (a), Pt/LDH-1 and Pt/LDH-AS catalysts (b)

图S3 使用后Pt/LDH-1(a, b)催化剂的TEM照片

Fig. S3 TEM images of the used Pt/LDH-1 (a, b) catalyst

图S4 Pt/LDH-1催化剂选择性加氢机理

Fig. S4 Summary of the selective hydrogenation mechanism of Pt/LDH-1 catalyst represents Mg2+, represents Al3+, represents Pt

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不同形貌MgAl LDH的制备及Pt/LDH的催化加氢性能

Preparation of MgAl LDH with Various Morphologies and Catalytic Hydrogenation Performance of Pt/LDH Catalysts

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