Ga2O3 modified CuCeO catalysts for CO2 hydrogenation to methanol

doi:10.11949/0438-1157.20250229

Abstract

Abstract:

It is an effective way to mitigate global warming and achieve carbon resources reuse by CO₂ hydrogenation to methanol. Cu/CeO₂ is an important catalyst for CO₂ hydrogenation to methanol, but the methanol selectivity still needs to be further improved. In this work, the xGaCuCeO catalysts with different amounts of Ga₂O₃ were prepared to modify its catalytic activities. The results show that Ga₂O₃ enhances the adsorption strength of CO₂ on the catalyst surface and increases the oxygen vacancy content on the catalyst surface, thereby improving the methanol selectivity of xGaCuCeO catalysts. Compared with the CuCeO catalyst, the 0.07GaCuCeO catalyst with Ga content of 1.1% (mass) has increased the selectivity of methanol by 47% and space-time yield by 26% (22.4 g·kg^-1·h^-1).

Key words: carbon dioxide, hydrogenation, synthesis of methanol, selectivity

摘要：

CO₂加氢制甲醇是缓解全球气候变暖、实现碳资源再利用的有效途径。Cu/CeO₂催化剂是CO₂加氢制甲醇的一类重要催化剂，但其甲醇选择性仍有待进一步提高。本文通过引入不同含量的Ga₂O₃制备了xGaCuCeO催化剂，以调控其甲醇选择性。研究结果显示，Ga₂O₃增强了催化剂表面CO₂的吸附强度，提高了催化剂表面氧空位含量，从而提高了xGaCuCeO催化剂的甲醇选择性。在260℃和3.0 MPa条件下，与CuCeO催化剂相比，Ga含量为1.1% （质量分数）的0.07GaCuCeO催化剂的甲醇选择性提高了47%，时空产率提高了26% （22.4 g·kg^-1·h^-1）。

关键词: 二氧化碳, 加氢, 合成甲醇, 选择性

CLC Number:

TQ 426.8

Yuntao ZHOU, Lifeng CUI, Jie ZHANG, Fuhong YU, Xingang LI, Ye TIAN. Ga₂O₃ modified CuCeO catalysts for CO₂ hydrogenation to methanol[J]. CIESC Journal, 2025, 76(8): 4042-4051.

周运桃, 崔丽凤, 张杰, 于富红, 李新刚, 田野. Ga₂O₃调控CuCeO催化CO₂加氢制甲醇的研究[J]. 化工学报, 2025, 76(8): 4042-4051.

Figures/Tables 10

Fig.1 XRD patterns of the CeO2, CuCeO and xGaCuCeO (x = 0.03,0.07,0.14) catalysts

Table 1 The composition and physical parameters of the catalysts

催化剂	Cu/%(质量)^①	Ga/%(质量)^①	颗粒尺寸/nm^②	比表面积/(m²·g^-1)	平均孔体积/(cm³·g^-1)	平均孔径/nm
CuCeO	14.3	0	7.9	35.0	0.4	44.0
0.03GaCuCeO	14.0	0.5	10.3	33.5	0.3	34.6
0.07GaCuCeO	13.9	1.1	11.0	29.1	0.2	35.7
0.14GaCuCeO	13.4	2.3	14.0	28.1	0.3	43.6

Fig.2 N2 adsorption-desorption isotherms for the reduced CuCeO and xGaCuCeO (x = 0.03,0.07,0.14) catalysts

Fig.3 TEM image[(a)—(d)], HRTEM image[(e)—(h)] and element mappings[(i)—(l)] of Cu, Ce, Ga, O for CuCeO and xGaCuCeO (x = 0.03,0.07,0.14) catalysts (each line from left to right are the CuCeO, 0.03GaCuCeO, 0.07GaCuCeO and 0.14GaCuCeO)

Fig.4 CuCeO and xGaCuCeO (x = 0.03,0.07,0.14) catalysts reduction and CO2 adsorption

Table 2 The parameters of CO2 adsorption and surface chemical valence state for catalysts

催化剂	T_β/℃	CO₂吸附量/(μmol·g^-1)	Ce³⁺/( Ce³⁺+ Ce⁴⁺)	O_ads/(O_ads+O_lat)	I₅₈₀/I₄₅₀
CuCeO	378	20.1	13.7	32.5	0.64
0.03GaCuCeO	391	15.9	14.4	35.1	0.68
0.07GaCuCeO	408	12.5	15.6	36.8	0.72
0.14GaCuCeO	410	11.3	18.2	38.6	0.79

Fig.5 XPS spectra of CuCeO and xGaCuCeO (x = 0.03,0.07,0.14) catalysts

Fig.6 Raman spectra of CuCeO and xGaCuCeO (x = 0.03,0.07,0.14) catalysts

Fig.7 CuCeO and xGaCuCeO (x = 0.03,0.07,0.14) catalysts activities test

Table 3 Comparison of different CeO2-based catalysts for CO2 hydrogenation to methanol

催化剂	温度/ ℃	压力/MPa	CO₂ 转化率/%	CH₃OH 选择性/%	文献
Cu/CeO₂	250	3.0	1.6	50.0	[29]
Pd/CeO₂	240	3.0	6.2	30.0	[30]
Cu0.3Zr0.3Ce	240	3.0	4.1	55.3	[31]
Ga_7.5Cu_7.5	225	5.0	3.1	55.0	[32]
0.03GaCuCeO	240	3.0	2.8	61.2	本工作
0.07GaCuCeO	220	3.0	1.6	77.6	本工作
0.14GaCuCeO	220	3.0	1.8	81.6	本工作

References 33

[1]	阳平坚, 彭栓, 王静, 等. 碳捕集、利用和封存(CCUS)技术发展现状及应用展望[J]. 中国环境科学, 2024, 44(1): 404-416.
	Yang P J, Peng S, Wang J, et al. Carbon capture, utilization and storage(CCUS) technology development status and application prospects[J]. China Environmental Science, 2024, 44(1): 404-416.
[2]	Nagireddi S, Agarwal J R, Vedapuri D. Carbon dioxide capture, utilization, and sequestration: current status, challenges, and future prospects for global decarbonization[J]. ACS Engineering Au, 2024, 4(1): 22-48.
[3]	Hu J T, Cai Y F, Xie J H, et al. Selectivity control in CO₂ hydrogenation to one-carbon products[J]. Chem, 2024, 10(4): 1084-1117.
[4]	De S, Dokania A, Ramirez A, et al. Advances in the design of heterogeneous catalysts and thermocatalytic processes for CO₂ utilization[J]. ACS Catalysis, 2020, 10(23): 14147-14185.
[5]	Kaliyaperumal A, Gupta P, Prasad Y S S, et al. Recent progress and perspective of the electrochemical conversion of carbon dioxide to alcohols[J]. ACS Engineering Au, 2023, 3(6): 403-425.
[6]	Ganji P, Chowdari R K, Likozar B. Photocatalytic reduction of carbon dioxide to methanol: carbonaceous materials, kinetics, industrial feasibility, and future directions[J]. Energy & Fuels, 2023, 37(11): 7577-7602.
[7]	贾晨喜, 邵敬爱, 白小薇, 等, 二氧化碳加氢制甲醇铜基催化剂性能的研究进展 [J]. 化工进展, 2020, 39(9): 3658-3668.
	Jia C X, Shao J A, Bai X W, et al. Review on Cu-based catalysts for CO₂ hydrogenation to methanol[J]. Chemical Industry and Engineering Progress, 2020, 39(9): 3658-3668.
[8]	时永兴, 林刚, 孙晓航, 等. 二氧化碳加氢制甲醇过程中铜基催化剂活性位点研究进展[J]. 化工进展, 2023, 42(S1): 287-298.
	Shi Y X, Lin G, Sun X H, et al. Research progress on active sites in Cu-based catalysts for CO₂ hydrogenation to methanol[J]. Chemical Industry and Engineering Progress, 2023, 42(S1): 287-298.
[9]	Liu X Y, Wang H W, Lu J L. Recent progress in understanding the nature of active sites for methanol synthesis over Cu/ZnO catalysts[J]. Journal of Catalysis, 2024, 436: 115561.
[10]	Singh R, Pandey V, Pant K K. Promotional role of oxygen vacancy defects and Cu-Ce interfacial sites on the activity of Cu/CeO₂ catalyst for CO₂ hydrogenation to methanol[J]. ChemCatChem, 2022, 14(24): e202201053.
[11]	Jiang F, Jiang F, Wang S S, et al. Catalytic activity for CO₂ hydrogenation is linearly dependent on generated oxygen vacancies over CeO₂-supported Pd catalysts[J]. ChemCatChem, 2022, 14(16): e202200422.
[12]	Chang K, Zhang H C, Cheng M J, et al. Application of ceria in CO₂ conversion catalysis[J]. ACS Catalysis, 2020, 10(1): 613-631.
[13]	周运桃, 王洪星, 李新刚, 等. CeO₂载体在CO₂加氢制甲醇中的应用和研究进展[J]. 化工进展, 2024, 43(5): 2723-2738.
	Zhou Y T, Wang H X, Li X G, et al. Application and research progress of CeO₂ support in CO₂ hydrogenation to methanol[J]. Chemical Industry and Engineering Progress, 2024, 43(5): 2723-2738.
[14]	Hengne A M, Yuan D J, Date N S, et al. Preparation and activity of copper-gallium nanocomposite catalysts for carbon dioxide hydrogenation to methanol[J]. Industrial & Engineering Chemistry Research, 2019, 58(47): 21331-21340.
[15]	Yang C S, Ma S C, Liu Y M, et al. Homolytic H₂ dissociation for enhanced hydrogenation catalysis on oxides[J]. Nature Communications, 2024, 15(1): 540.
[16]	Dai H, Zhang A H, Xiong S Q, et al. The catalytic performance of Ga₂O₃-CeO₂ composite oxides over reverse water gas shift reaction[J]. ChemCatChem, 2022, 14(6): e202200049.
[17]	Wang J J, Tang C Z, Li G N, et al. High-performance M_aZrO _x (M_a = Cd, Ga) solid-solution catalysts for CO₂ hydrogenation to methanol[J]. ACS Catalysis, 2019, 9(11): 10253-10259.
[18]	Sha F, Tang C Z, Tang S, et al. The promoting role of Ga in ZnZrO _x solid solution catalyst for CO₂ hydrogenation to methanol[J]. Journal of Catalysis, 2021, 404: 383-392.
[19]	Feng W H, Yu M M, Wang L J, et al. Insights into bimetallic oxide synergy during carbon dioxide hydrogenation to methanol and dimethyl ether over GaZrO _x oxide catalysts[J]. ACS Catalysis, 2021, 11(8): 4704-4711.
[20]	黄静静, 蔡金孟, 马奎, 等. Ga₂O₃改性Cu/SiO₂催化剂降低水蒸气催化重整产物中CO选择性[J]. 物理化学学报, 2019, 35(4): 431-441.
	Huang J J, Cai J M, Ma K, et al. Ga₂O₃-modified Cu/SiO₂ catalysts with low CO selectivity for catalytic steam reforming[J]. Acta Physico-Chimica Sinica, 2019, 35(4): 431-441.
[21]	Deng B W, Song H, Peng K, et al. Metal-organic framework-derived Ga-Cu/CeO₂ catalyst for highly efficient photothermal catalytic CO₂ reduction[J]. Applied Catalysis B: Environmental, 2021, 298: 120519.
[22]	Li H J, Xiao Y H, Xiao J L, et al. Selective hydrogenation of CO₂ into dimethyl ether over hydrophobic and gallium-modified copper catalysts[J]. Chinese Journal of Catalysis, 2023, 54: 178-187.
[23]	Singh R, Tripathi K, Pant K K. Investigating the role of oxygen vacancies and basic site density in tuning methanol selectivity over Cu/CeO₂ catalyst during CO₂ hydrogenation[J]. Fuel, 2021, 303: 121289.
[24]	戴文华, 辛忠, Si掺杂对Cu/ZrO 2 催化CO₂加氢制甲醇性能的影响[J]. 化工学报, 2022, 73(8): 3586-3596.
	Dai W H, Xin Z. Effect of Si-doped Cu/ZrO₂ on the performance of catalysts for CO₂ hydrogenation to methanol[J]. CIESC Journal, 2022, 73(8): 3586-3596
[25]	张家琳, 徐大为, 高越, 等. 泡沫镍负载CeO₂改性CuO催化剂的碳烟燃烧性能研究[J]. 化工学报, 2024, 75(1): 312-321.
	Zhang J L, Xu D W, Gao Y, et al. Performance of soot combustion over CeO₂ modified CuO catalysts supported on nickel foams[J]. CIESC Journal, 2024, 75(1): 312-321.
[26]	Gómez D, Vergara T, Ortega M, et al. Interdependence between the extent of Ga promotion, the nature of active sites, and the reaction mechanism over Cu catalysts for CO₂ hydrogenation to methanol[J]. ACS Catalysis, 2024, 14(20): 15265-15278.
[27]	Lam E, Noh G, Chan K W, et al. Enhanced CH₃OH selectivity in CO₂ hydrogenation using Cu-based catalysts generated via SOMC from Ga^Ⅲ single-sites[J]. Chemical Science, 2020, 11(29): 7593-7598.
[28]	Zhang Y D, Liang L, Chen Z Y, et al. Highly efficient Cu/CeO₂-hollow nanospheres catalyst for the reverse water-gas shift reaction: investigation on the role of oxygen vacancies through in situ UV-Raman and DRIFTS[J]. Applied Surface Science, 2020, 516: 146035.
[29]	Zhu J D, Su Y Q, Chai J C, et al. Mechanism and nature of active sites for methanol synthesis from CO/CO₂ on Cu/CeO₂ [J]. ACS Catalysis, 2020, 10(19): 11532-11544.
[30]	Jiang F, Wang S S, Liu B, et al. Insights into the influence of CeO₂crystal facet on CO₂hydrogenation to methanol over Pd/CeO₂catalysts[J]. ACS Catalysis, 2020, 10(19): 11493-11509.
[31]	Zhang J P, Sun X H, Wu C Y, et al. Engineering Cu⁺/CeZrO _x interfaces to promote CO₂ hydrogenation to methanol[J]. Journal of Energy Chemistry, 2023, 77: 45-53.
[32]	Attada Y, Velisoju V K, Mohamed H O, et al. Dual experimental and computational approach to elucidate the effect of Ga on Cu/CeO₂-ZrO₂ catalyst for CO₂ hydrogenation[J]. Journal of CO₂ Utilization, 2022, 65: 102251.
[33]	Han X Y, Xiao T T, Li M S, et al. Synergetic interaction between single-atom Cu and Ga₂O₃ enhances CO₂ hydrogenation to methanol over CuGaZrO _x [J]. ACS Catalysis, 2023, 13(20): 13679-13690.

Related Articles 15

[1]	Jichao GUO, Xiaoxiao XU, Yunlong SUN. Airflow simulation and optimization based on $C O 2$ concentration in plant factory [J]. CIESC Journal, 2025, 76(S1): 237-245.
[2]	Xingliang PEI, Cuiping YE, Yingli PEI, Wenying LI. Selective adsorption and separation of xylene isomers by alkali-modified MIL-53(Cr) [J]. CIESC Journal, 2025, 76(S1): 258-267.
[3]	Fanchen KONG, Shuo ZHANG, Mingsheng TANG, Huiming ZOU, Zhouhang HU, Changqing TIAN. Simulation of gas bearings in carbon dioxide linear compressors [J]. CIESC Journal, 2025, 76(S1): 281-288.
[4]	Ting HE, Kai ZHANG, Wensheng LIN, Liqiong CHEN, Jiafu CHEN. Research on integrated process of cryogenic CO₂ removal under supercritical pressure and liquefaction for biogas [J]. CIESC Journal, 2025, 76(S1): 418-425.
[5]	Xiayu FAN, Jianchen SUN, Keying LI, Xinya YAO, Hui SHANG. Machine learning drives system optimization of liquid organic hydrogen storage technology [J]. CIESC Journal, 2025, 76(8): 3805-3821.
[6]	Min YANG, Xinwei DUAN, Junhong WU, Jie MI, Jiancheng WANG, Mengmeng WU. COS catalyzed hydrolysis performance and deactivation mechanism of Sm₂O₃/γ-Al₂O₃ catalysts [J]. CIESC Journal, 2025, 76(8): 4061-4070.
[7]	Qinwen LIU, Hengbing YE, Yiwei ZHANG, Fahua ZHU, Wenqi ZHONG. Study on pressurized oxy-fuel co-combustion characteristics of coal and poultry litter [J]. CIESC Journal, 2025, 76(7): 3487-3497.
[8]	Zeming DONG, Juwei LOU, Nan WANG, Liangqi CHEN, Jiangfeng WANG, Pan ZHAO. Research on thermodynamic properties of supercritical compressed carbon dioxide energy storage system with waste heat recovery [J]. CIESC Journal, 2025, 76(7): 3477-3486.
[9]	Zhenning FAN, Haining LIANG, Maoli FANG, Yifan HE, Shuai YU, Xingqing YAN, Jiaran AN, Fanfan QIAO, Jianliang YU. Research and comparison of throttling and venting characteristics of CO₂ pipelines in different phase states [J]. CIESC Journal, 2025, 76(7): 3742-3751.
[10]	Hongxin DING, Wenxiang GAN, Yongyang ZHAO, Runze JIA, Ziqi KANG, Yulong ZHAO, Yong XIANG. Corrosion mechanisms of X65 steel welded joints in supercritical CO₂ and H₂O-rich phases [J]. CIESC Journal, 2025, 76(7): 3426-3435.
[11]	Fengfeng GAO, Huifeng CHENG, Bo YANG, Xiaogang HAO. Electrically driven NiFeMn LDH/CNTs/PVDF film electrode for selective extraction of tungstate ions [J]. CIESC Journal, 2025, 76(7): 3350-3360.
[12]	Lili LU, Chen LI, Liuyun CHEN, Xinling XIE, Xuan LUO, Tongming SU, Zuzeng QIN, Hongbing JI. Morphology regulation of BiOBr and study on its performance of photocatalytic CO₂ reduction [J]. CIESC Journal, 2025, 76(6): 2687-2700.
[13]	Yaohui ZHANG, Yujie BAN, Weishen YANG. Vapor-phase synthesis and post-synthetic modification of metal-organic framework membranes [J]. CIESC Journal, 2025, 76(5): 2070-2086.
[14]	Zehai XU, Chao LIU, Guoliang ZHANG. Hydrophobic pervaporation membranes on polymer substrate for solvent recovery [J]. CIESC Journal, 2025, 76(5): 2055-2069.
[15]	Yujie MAO, Xiaofei LU, Xian SUO, Lifeng YANG, Xili CUI, Huabin XING. Advances in research on catalysts for deep removal of trace oxygen in industrial gases [J]. CIESC Journal, 2025, 76(5): 1997-2010.

Ga₂O₃ modified CuCeO catalysts for CO₂ hydrogenation to methanol

Ga₂O₃调控CuCeO催化CO₂加氢制甲醇的研究

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 33

Related Articles 15

Recommended Articles

Metrics

Comments