NH2-UIO-66负载RuCuMo纳米催化剂的制备及其催化产氢

doi:10.15541/jim20190903

无机材料学报 ›› 2019, Vol. 34 ›› Issue (12): 1316-1324.DOI: 10.15541/jim20190903

NH₂-UIO-66负载RuCuMo纳米催化剂的制备及其催化产氢

张翊青,刘梨,张淑娟,万正睿,刘红英,周立群()

湖北大学化学化工学院, 有机化工新材料湖北省协同创新中心, 有机功能分子合成与应用教育部重点实验室, 武汉430062

收稿日期:2019-03-01 修回日期:2019-03-28 出版日期:2019-12-20 网络出版日期:2019-12-02
作者简介:张翊青(1995-), 女, 硕士研究生. E-mail: zhangyq95@163.com
基金资助:
湖北省自然科学基金(2010CDB04701);湖北省教育厅重点项目(D20101011);有机功能分子合成与应用教育部重点实验室项目(2016-KL-007);湖北省大学生创新创业训练项目(201510512030)

Preparation and Dehydrogenation Property of NH₂-UIO-66 Supported RuCuMo Nanocatalyst

ZHANG Yi-Qing,LIU Li,ZHANG Shu-Juan,WAN Zheng-Rui,LIU Hong-Ying,ZHOU Li-Qun()

Hubei Collaborative Innovation Center for Advanced Organic Chemical Materials, Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules, College of Chemistry and Chemical Engineering, Hubei University, Wuhan 430062,China

Received:2019-03-01 Revised:2019-03-28 Published:2019-12-20 Online:2019-12-02
Supported by:
Hubei Provincial Natural Science Foundation(2010CDB04701);Hubei Province Education Office Key Research(D20101011);Ministry of Education Key Laboratory for the Synthesis and Application of Organic Functional Molecules(2016-KL-007);Hubei College Students' Innovation Training Program of China(201510512030)

摘要/Abstract

摘要：

采用锆盐和2-氨基对苯二甲酸以溶剂热法成功制备了氨基化的金属有机骨架化合物NH₂-UIO-66, 并利用浸渍还原法成功负载RuCuMo纳米粒子, 制备了RuCuMo@NH₂-UIO-66催化剂。通过X射线粉末衍射仪(XRD)、透射电子显微镜(TEM)、场发射扫描电镜(SEM)等技术对NH₂-UIO-66、RuCuMo@NH₂-UIO-66的结构、形貌、组成和比表面积进行了表征, 并对载体、多金属负载型催化剂以及无载体的RuCuMo纳米粒子的产氢性能进行了分析。结果显示, Ru₁Cu₂Mo_0.5@NH₂-UIO-66催化剂的催化活性最高, 引入Cu和Mo能显著增强Ru对氨硼烷水解产氢的催化活性。这主要归因于RuCuMo纳米粒子之间强的协同作用, RuCuMo纳米粒子与载体NH₂-UIO-66间的双功能效应, 以及MOFs上氨基的锚锭作用, 可以阻止金属粒子的团聚, 促进超细粒子的形成。催化反应的活化能(E_a)为30.1 kJ?mol ^-1, 转化频率(TOF)为180.83 $\text{mo}{{\text{l}}_{{{\text{H}}_{2}}}}\cdot \text{mol}_{\text{Ru}}^{-1}\cdot {{\min }^{-1}}$, 非贵金属Cu和Mo的引入为催化活性的提高和工业应用提供了重要的研究价值。

关键词: 金属有机骨架(NH₂-UIO-66), RuCuMo@NH₂-UIO-66, 溶剂热法, 协同催化, 产氢性能

Abstract:

Amine-functionalize metal organic framework (NH₂-UIO-66) was successfully synthesized by solvothermal method with zirconium salt and 2-aminoterephtalic acid. Tri-metallic RuCuMo nanoparticles (NPs) were immobilized by a facile impregnation-reduction method to prepare RuCuMo@NH₂-UIO-66 catalysts. The structure, morphology, composition and specific surface area of the above catalysts were characterized. Ru₁Cu₂Mo_0.5@NH₂-UIO-66 catalyst exhibits the highest catalytic activity comparing with Ru, RuCu and CuMo counterparts as well as pure tri-metallic RuCuMo NPs in hydrolytic dehydrogenation of ammonia borane at room temperature, and the correspoding activation energy (E_a) and turnover frequency values (TOF) are 30.1 kJ?mol ^-1 and 180.83 mol H₂ min ^-1(mol Ru) ^-1, respectively. Addition of Cu and Mo can significantly enhance the catalytic activity of Ru counterparts, owing to the synergistic effect among Ru, Cu and Mo atoms, bi-functional effect generated between RuCuMo NPs and NH₂-UIO-66 support, and the amine as anchoring groups in the NH₂-UIO-66 framework, which facilitate the formation and stabilization of ultra-small RuCuMo NPs by preventing their aggregation. The addition of non-noble metals Cu and Mo provides an important approach for the improvement of catalytic activity and industrial application.

Key words: metal organic frameworks (NH₂-UIO-66), RuCuMo@NH₂-UIO-66, solvothermal method, synergistic catalysis, releasing hydrogen

中图分类号:

O643

张翊青, 刘梨, 张淑娟, 万正睿, 刘红英, 周立群. NH₂-UIO-66负载RuCuMo纳米催化剂的制备及其催化产氢[J]. 无机材料学报, 2019, 34(12): 1316-1324.

ZHANG Yi-Qing, LIU Li, ZHANG Shu-Juan, WAN Zheng-Rui, LIU Hong-Ying, ZHOU Li-Qun. Preparation and Dehydrogenation Property of NH₂-UIO-66 Supported RuCuMo Nanocatalyst[J]. Journal of Inorganic Materials, 2019, 34(12): 1316-1324.

图/表 9

图1 NH2-UIO-66、Ru@NH2-UIO-66、CuMo@NH2-UIO-66、RuCu@NH2-UIO-66和Ru1Cu2Mo0.5@NH2-UIO-66的XRD图谱

Fig. 1 XRD patterns of NH2-UIO-66, Ru@NH2-UIO-66, CuMo@NH2-UIO-66, RuCu@NH2-UIO-66 and Ru1Cu2Mo0.5@NH2-UIO-66

图2 (a,b) NH2-UIO-66、(c) Ru1Cu2Mo0.5@NH2-UIO-66、(e) RuCuMo纳米粒子的TEM照片; (d) Ru1Cu2Mo0.5@NH2-UIO-66和(f) RuCuMo纳米粒子的粒径分布图

Fig. 2 TEM images of (a, b) NH2-UIO-66, (c) Ru1Cu2Mo0.5@NH2-UIO-66, (e) RuCuMo NPs, (d, f) particle size distributions of (d) Ru1Cu2Mo0.5@NH2-UIO-66 and (f) RuCuMo NPs

图3 (a, c) Ru1Cu2Mo0.5@NH2-UIO-66的场发射扫描电镜照片, (b) EDS能谱分析和(d~f)相应的元素分布图像

Fig. 3 (a, c) FESEM image, (b) EDS analysis of Ru1Cu2Mo0.5@NH2-UIO-66 and (d-f) elemental mappings of Ru, Cu and Mo

图4 Ru1Cu2Mo0.5@NH2-UIO-66催化剂的XPS能谱图

Fig. 4 XPS spectra of the Ru1Cu2Mo0.5@NH2-UIO-66 catalysts survey, (b) Ru3p, (c)Cu2p, (d) Mo3d, (e)N1s

图5 NH2-UIO-66、Ru1Cu2Mo0.5@NH2-UIO-66和循环5次后Ru1Cu2Mo0.5@NH2-UIO-66的红外光谱图

Fig. 5 FT-IR spectra of NH2-UIO-66, Ru1Cu2Mo0.5@NH2-UIO- 66 and Ru1Cu2Mo0.5@NH2-UIO-66 after 5 runs

表1 ICP-AES对RuCuMo@NH2-UIO-66催化剂中的元素分析结果

Table 1 ICP-AES analyses of RuCuMo@NH2-UIO-66 catalysts with different molar ratios

Catalyst	Initial ratio of Ru : Cu : Mo	Actual ratio of Ru : Cu : Mo	Actual Ru loading/wt%
Ru₁Cu₂Mo_0.25@NH₂-UIO-66	1.00 : 2.00 : 0.25	1.00 : 2.20 : 0.04	4.89
Ru₁Cu₂Mo_0.5@NH₂-UIO-66	1.00 : 2.00 : 0.50	1.00 : 1.82 : 0.09	5.48
Ru₁Cu₂Mo_1.0@NH₂-UIO-66	1.00 : 2.00 : 1.00	1.00 : 2.04 : 0.19	5.16

图6 (a) RuCuMo纳米粒子, Ru@NH2-UIO-66+Cu@NH2- UIO-66+Mo@NH2-UIO-66, Ru@NH2-UIO-66; Ru1Cu2@NH2-UIO-66, CuMo@NH2-UIO-66, Ru1Cu2Mo0.5@NH2-UIO- 66, NH2-UIO-66; (b) Ru1Cux Mo0.5@NH2-UIO-66和(c)Ru1Cu2 Moy@NH2-UIO-66的氨硼烷水解产氢速率曲线

Fig. 6 Plots of time vs. n(H2)/n(NH3BH3) from the hydrolysis of AB (18.5 mg): (a) RuCuMo NPs, Ru@NH2-UIO-66+Cu@NH2-UIO-66+Mo@NH2-UIO-66, Ru@NH2-UIO-66, Ru1Cu2 @NH2-UIO-66, CuMo@NH2-UIO-66, Ru1Cu2Mo0.5@NH2-UIO-66, NH2-UIO-66; (b) Ru1CuxMo0.5@NH2-UIO-66, and (c) Ru1Cu2Moy@NH2-UIO-66

表2 不同钌基催化剂用于AB水解脱氢的催化活性

Table 2 Catalytic activities of different Ru-based catalysts used for the hydrolytic dehydrogenation of AB

Catalyst	TOF/($\text{mo}{{\text{l}}_{{{\text{H}}_{2}}}}\cdot \text{mol}_{\text{Ru}}^{-1}\cdot {{\min }^{-1}}$)	E_a/(kJ?mol^-1)	Ref.
Ru NPs	26.70	66.50	[34]
RuCu(1:1)/γ-Al₂O₃	16.40	52.00	[35]
RuCo(1:1)/γ-Al₂O₃	32.90	47.00	[35]
Ru(0)/TiO₂	241.00	70.00	[36]
RuCo@MIL-53	87.24	34.32	[16]
Ru@g-C₃N₄	313.00	37.40	[37]
RuCu/graphene	135.00	30.60	[38]
RuCuMo@NH₂-UIO-66	180.83	30.10	This study

图7 温度对Ru1Cu2Mo0.5@NH2-UIO-66催化水解氨硼烷的影响曲线(a)及其相应的阿伦尼乌斯图(b), Ru1Cu2Mo0.5@NH2-UIO-66的5次循环稳定性图(c)

Fig. 7 Plots of time vs. n(H2)/n(NH3BH3) for the hydrolysis of AB (18.5 mg) aqueous solution catalyzed by Ru1Cu2Mo0.5@NH2-UIO-66 at different temperatures(a), and the corresponding Arrhenius plot (b), and reusability test for the Ru1Cu2Mo0.5@NH2-UIO-66 within five cycles(c)

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NH₂-UIO-66负载RuCuMo纳米催化剂的制备及其催化产氢

Preparation and Dehydrogenation Property of NH₂-UIO-66 Supported RuCuMo Nanocatalyst

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