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

doi:10.6023/cjoc202406017

Chinese Journal of Organic Chemistry ›› 2024, Vol. 44 ›› Issue (10): 3223-3232.DOI: 10.6023/cjoc202406017 Previous Articles Next Articles

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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

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
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: *E-mail: wanghx@tust.edu.cn;qianql@iccas.ac.cn;hanbx@iccas.ac.cn
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)

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

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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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Fig. & Tab. 16

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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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纳米花状Ir/MoS2催化剂用于CO2加氢高选择性制备甲酸盐