纳米花状Ir/MoS2催化剂用于CO2加氢高选择性制备甲酸盐

doi:10.6023/cjoc202406017

有机化学 ›› 2024, Vol. 44 ›› Issue (10): 3223-3232.DOI: 10.6023/cjoc202406017 上一篇下一篇

研究论文

纳米花状Ir/MoS₂催化剂用于CO₂加氢高选择性制备甲酸盐

何君^a, 王红星^a^,^*(), 余成龙^b^,^c, 张艳茹^b^,^c, 王莹^b, 王燕燕^b^,^c, 张龙博^b^,^c, 郭佳^b^,^c, 钱庆利^b^,^c^,^*(), 韩布兴^b^,^c^,^d^,^*()

a 天津科技大学化工与材料学院天津 300457
b 中国科学院化学研究所胶体、界面与化学热力学实验室北京 100190
c 中国科学院大学化学科学学院北京 100049
d 华东师范大学化学与分子工程学院石油分子与过程工程国家重点实验室上海市绿色化学与化工过程重点实验室上海 200062

收稿日期:2024-06-12 修回日期:2024-07-29 发布日期:2024-08-30
通讯作者: 王红星, 钱庆利, 韩布兴
基金资助:
国家自然科学基金(22033009); 国家自然科学基金(22293015); 国家自然科学基金(22072156); 国家自然科学基金(22073104); 国家自然科学基金(22121002); 国家重点研发计划(2022YFA1504904)

Nanoflower-Shaped Ir/MoS₂ Catalyst for Highly Selective Production of Formate by CO₂ Hydrogenation

Jun He^a, Hongxing Wang^a(), Chenglong Yu^b^,^c, Yanru Zhang^b^,^c, Ying Wang^b, Yanyan Wang^b^,^c, Longbo Zhang^b^,^c, Jia Guo^b^,^c, Qingli Qian^b^,^c(), Buxing Han^b^,^c^,^d()

a College of Chemical Engineering and Materials Science, Tianjin University of Science and Technology, Tianjin 300457
b Laboratory of Colloid and Interface and Thermodynamics, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190
c School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing 100049
d Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062

Received:2024-06-12 Revised:2024-07-29 Published:2024-08-30
Contact: Hongxing Wang, Qingli Qian, Buxing Han
Supported by:
National Science Foundation of China(22033009); National Science Foundation of China(22293015); National Science Foundation of China(22072156); National Science Foundation of China(22073104); National Science Foundation of China(22121002); National Key Research and Development Program of China(2022YFA1504904)

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摘要/Abstract

基于简单的水热合成法制备了一系列不同Ir负载量的纳米花状的X% Ir/MoS₂催化剂, 探究其在CO₂加氢反应中的催化活性. Ir/MoS₂催化剂呈现出纳米花状的形貌, 直径大约为800 nm, 纳米花上的二维纳米片分布良好, 这有利于活性位点的充分暴露. Ir的掺杂有效地调整了催化剂的电子结构, 能够使MoS₂局部结构发生相变. 在较低的反应压力下, 1% Ir/MoS₂催化剂表现出了最高的甲酸盐选择性(98%)和活性(8.6 mmol•g^–1•h^–1), 但是过量Ir的负载会导致Ir纳米颗粒发生团聚, 降低了产物的选择性和活性. 1% Ir/MoS₂催化剂还表现出优异的催化稳定性, 在重复使用3次后催化活性没有显著降低. 还通过控制实验对催化机理和反应的溶剂效应进行了研究和讨论. 本研究为开发高性能的CO₂加氢合成甲酸/甲酸盐催化剂提供了一条新的途径.

关键词: CO₂加氢, 甲酸/甲酸盐, 纳米花, 催化剂, Ir/MoS₂

A series of nanoflower-shaped X% Ir/MoS₂ catalysts with different Ir loadings were prepared based on a simple hydrothermal synthesis method and their catalytic activities in CO₂ hydrogenation were investigated. The Ir/MoS₂ catalyst has a nanoflower-like shape with a diameter of about 800 nm. The layers of two-dimensional nanosheets on the catalyst were well dispersed, which increased the exposure of the active sites. The doping of Ir could effectively tune the electronic structure of the catalyst, causing the local structure phase change of MoS₂. Under low reaction pressure, the 1% Ir/MoS₂ composite showed the highest formate selectivity (98%) and activity (8.6 mmol•g^–1•h^–1). The excessive Ir loading would lead to the agglomeration of Ir to form nanoparticles, which reduced the selectivity and activity of product. The 1% Ir/MoS₂ catalyst also showed excellent catalytic stability, and the catalytic activity did not decrease obviously after being reused three times. Based on control experiments, the catalytic mechanism and solvent effect were also studied and discussed. This study provid es a new way for developing high-performance catalysts for CO₂ hydrogenation to formate.

Key words: CO₂ hydrogenation, formate, nanoflower, catalyst, Ir/MoS₂

引用此文

何君, 王红星, 余成龙, 张艳茹, 王莹, 王燕燕, 张龙博, 郭佳, 钱庆利, 韩布兴. 纳米花状Ir/MoS₂催化剂用于CO₂加氢高选择性制备甲酸盐[J]. 有机化学, 2024, 44(10): 3223-3232.

Jun He, Hongxing Wang, Chenglong Yu, Yanru Zhang, Ying Wang, Yanyan Wang, Longbo Zhang, Jia Guo, Qingli Qian, Buxing Han. Nanoflower-Shaped Ir/MoS₂ Catalyst for Highly Selective Production of Formate by CO₂ Hydrogenation[J]. Chinese Journal of Organic Chemistry, 2024, 44(10): 3223-3232.

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图/表 16

图1. MoS2和不同Ir负载量X% Ir/MoS2催化剂的XRD图谱

Figure 1. XRD patterns of MoS2 and X% Ir/MoS2 catalysts with different Ir loadings

图2. (a) MoS2, (b) 1% Ir/MoS2, (c) 3% Ir/MoS2, (d) 5% Ir/MoS2及(e) 10% Ir/MoS2的SEM图像

Figure 2. SEM images of (a) MoS2, (b) 1% Ir/MoS2, (c) 3% Ir/MoS2, (d) 5% Ir/MoS2 and (e) 10% Ir/MoS2

图3. (a) MoS2、(b) 1% Ir/MoS2和(c) 10% Ir/MoS2催化剂的TEM图像, (d) 1% Ir/MoS2的STEM图像和元素分布结果以及(e) 1% Ir/ MoS2和(f) 10% Ir/MoS2的HAADF-STEM图像

Figure 3. TEM images of (a) MoS2, (b) 1% Ir/MoS2 and (c) 10% Ir/MoS2, (d) dark-field STEM image and element mapping results of 1% Ir/MoS2 catalyst, and HAADF-STEM images of (e) 1% Ir/MoS2 and (f) 10% Ir/MoS2

图4. MoS2, 1% Ir/MoS2和10% Ir/MoS2催化剂的XPS光谱图

Figure 4. XPS spectra of MoS2, 1% Ir/MoS2 and 10% Ir/MoS2 catalysts (a) Ir 4f, (b) Mo 3d, (c) S 2p

Catalyst	Actual loading/%
1% Ir/MoS₂	0.63
3% Ir/MoS₂	2.07
5% Ir/MoS₂	3.79
10% Ir/MoS₂	6.25

表1. ICP-OES测定的不同Ir负载量X% Ir/MoS2催化剂中Ir的含量

Table 1. Content of Ir in the X% Ir/MoS2 with different iridium loadings as detected by ICP-OES

图5. MoS2和1% Ir/MoS2催化剂的拉曼光谱图

Figure 5. Raman spectra of MoS2 and 1% Ir/MoS2 catalysts

Catalyst	S_BET/(m²•g^–1)	d_p/nm
MoS₂	12.7	13.2
1% Ir/MoS₂	9.1	13.1
10% Ir/MoS₂	8.9	12.7

表2. MoS2, 1% Ir/MoS2和10% Ir/MoS2催化剂的结构性质

Table 2. Structural properties of MoS2, 1% Ir/MoS2 and 10% Ir/MoS2

图6. MoS2, 1% Ir/MoS2和10% Ir/MoS2催化剂的(a~c) N2吸附脱附等温线和(d~f)孔径分布图

Figure 6. (a~c) N2 adsorption isotherms and (d~f) pore size distribution of MoS2, 1% Ir/MoS2 and 10% Ir/MoS2

图7. (a) MoS2表面负载不同种类的金属后的产物选择性及活性、(b) Ir负载于不同Mo基载体表面后的产物选择性及活性、(c) MoS2和不同Ir负载量X% Ir/MoS2催化剂的产物选择性及活性(反应条件: 2 mL 0.5 mol/L NaHCO3溶液, 初始压力为2 MPa, CO2/H2=1/3, 20 mg催化剂, 200 ℃反应6 h)、(d)反应温度对1% Ir/MoS2催化剂产物选择性及活性的影响及(e) 1% Ir/MoS2催化剂的循环稳定性测试结果

Figure 7. (a) Product selectivity and activity of different types of metal loaded on the MoS2 catalysts, (b) product selectivity and activity of different Mo compounds supported Ir catalyst, (c) product selectivity and activity of MoS2 and X% Ir/MoS2 catalysts with different Ir loadings during CO2 hydrogenation (2 mL of 0.5 mol/L aqueous NaHCO3 solution, initial pressure 2 MPa, CO2/H2=1/3, 20 mg of catalyst, at 200 ℃ for 6 h), (d) effect of reaction temperature on the CO2 hydrogenation using 1% Ir/MoS2, and (e) test of catalytic stability for 1% Ir/MoS2

图8. 1% Ir/MoS2催化剂反应后的(a) XRD图谱和(b) SEM图像

Figure 8. (a) XRD patterns and (b) SEM images of 1% Ir/MoS2 catalyst after reaction

图9. MoS2和1% Ir/MoS2的(a) CO2-TPD谱图、(b) H2-TPD谱图和(c) H2-TPR谱图

Figure 9. (a) CO2-TPD, (b) H2-TPD and (c) H2-TPR profiles of MoS2 and 1% Ir/MoS2 catalysts

图10. NaHCO3, Na2CO3和0.5 mol/L NaHCO3水溶液在空气中加热至沸腾后的13C NMR谱图

Figure 10. 13C NMR spectra of NaHCO3, Na2CO3 and 0.5 mol/L NaHCO3 aqueous solution after heating to boiling in air

图11. CO2加氢产物在THF, Diox和CH3CN溶剂中的1H NMR谱图

Figure 11. 1H NMR spectra of CO2 hydrogenation products in THF, Diox and CH3CN solvents Standard solutions (100 mmol/L HCOOH in the corresponding solvents) were used as reference

图12. 同位素标记实验所得到的1H NMR和2H NMR谱图

Figure 12. 1H NMR and 2H NMR spectra obtained from isotope labelling experiments (a) D2O as solvent, (b) D2O replacing half of the H2O as solvent. Dimethyl sulfoxide (DMSO) and DMSO-d6 as internal standards

图13. 不同质子溶剂中甲酸盐的反应活性

Figure 13. Formate activity in different protic solvents 200 ℃ for 6 h, 2 mL solvent, initial pressure 2 MPa, CO2/H2 (V∶V=1∶3), 20 mg of catalyst

图式1. 甲酸转化反应机理

Scheme 1. Reaction mechanism of formic acid conversion

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纳米花状Ir/MoS₂催化剂用于CO₂加氢高选择性制备甲酸盐

Nanoflower-Shaped Ir/MoS₂ Catalyst for Highly Selective Production of Formate by CO₂ Hydrogenation

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