Ga2O3调控CuCeO催化CO2加氢制甲醇的研究

doi:10.11949/0438-1157.20250229

摘要/Abstract

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

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

中图分类号:

TQ 426.8

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.

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.

图/表 10

图1 CeO2、CuCeO和xGaCuCeO (x = 0.03、0.07、0.14) 催化剂XRD谱图

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

表1 催化剂组成及物理参数

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

图2 还原后的CuCeO和xGaCuCeO (x = 0.03、0.07、0.14) 催化剂N2吸附-脱附等温线

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

图3 CuCeO和xGaCuCeO (x = 0.03、0.07、0.14)催化剂TEM图[（a）~（d）]；晶格条纹[（e）~（h）]；Cu、Ce、Ga、O四种元素面分布图像[（i）~（l）] (每行从左到右依次为CuCeO、0.03GaCuCeO、0.07GaCuCeO、0.14GaCuCeO)

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)

图4 CuCeO和xGaCuCeO (x = 0.03、0.07、0.14) 催化剂还原和CO2吸附

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

表2 催化剂CO2吸附和表面化学价态参数

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

图5 CuCeO和xGaCuCeO (x = 0.03、0.07、0.14)催化剂 XPS谱图

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

图6 CuCeO和xGaCuCeO (x = 0.03、0.07、0.14)催化剂Raman光谱

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

图7 CuCeO和xGaCuCeO (x = 0.03、0.07、0.14)催化剂活性测试

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

表3 CeO2基催化剂催化CO2 加氢制甲醇对比

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

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Ga₂O₃调控CuCeO催化CO₂加氢制甲醇的研究

Ga₂O₃ modified CuCeO catalysts for CO₂ hydrogenation to methanol

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