镓改性的铜基疏水催化剂用于CO2选择性加氢制二甲醚的研究

doi:10.1016/S1872-2067(23)64535-8

催化学报 ›› 2023, Vol. 54: 178-187.DOI: 10.1016/S1872-2067(23)64535-8

镓改性的铜基疏水催化剂用于CO₂选择性加氢制二甲醚的研究

李航杰^a, 肖月华^a, 肖佳乐^a, 范凯^b, 李炳宽^c, 李晓龙^c, 王亮^a^,^*(), 肖丰收^a

^a浙江大学化学与生物工程学院生物质化学工程教育部重点实验室, 浙江杭州310028
^b浙江大学化学系浙江省应用化学重点实验室, 浙江杭州310028
^c陕西瑞科新材料股份有限公司, 陕西宝鸡721306

收稿日期:2023-08-13 接受日期:2023-10-09 出版日期:2023-11-18 发布日期:2023-11-15
通讯作者: *电子信箱: liangwang@zju.edu.cn (王亮).
基金资助:
国家重点研发计划(2022YFA1503502);国家自然科学基金(22288101);国家自然科学基金(U21B20101);国家自然科学基金(22102142)

Selective hydrogenation of CO₂ into dimethyl ether over hydrophobic and gallium-modified copper catalysts

Hangjie Li^a, Yuehua Xiao^a, Jiale Xiao^a, Kai Fan^b, Bingkuan Li^c, Xiaolong Li^c, Liang Wang^a^,^*(), Feng-Shou Xiao^a

^aKey Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310028, Zhejiang, China
^bKey Laboratory of Applied Chemistry of Zhejiang Province, Department of Chemistry, Zhejiang University, Hangzhou 310028, Zhejiang, China
^cShaanxi Rock New Materials Co., Ltd., Baoji 721306, Shaanxi, China

Received:2023-08-13 Accepted:2023-10-09 Online:2023-11-18 Published:2023-11-15
Contact: *E-mail: liangwang@zju.edu.cn (L. Wang).
Supported by:
National Key Research and Development Program of China(2022YFA1503502);National Natural Science Foundation of China(22288101);National Natural Science Foundation of China(U21B20101);National Natural Science Foundation of China(22102142)

摘要/Abstract

摘要：

CO₂选择性加氢制二甲醚(DME)是实现CO₂资源化利用的重要途径之一. 然而, 该过程面临着多方面的挑战. 比如, 水分子会限制CO₂的高效转化并诱导铜颗粒的团聚, 导致催化活性与稳定性不足. 此外, 沸石分子筛甲醇脱水催化剂的酸性过强容易造成甲醇过度脱水生成低碳烃, 导致催化选择性不足. 因此, 开发高效稳定的CO₂加氢制DME催化剂十分必要.

本文通过共水解法制备了一系列镓改性的疏水二氧化硅负载铜基催化剂, 并通过优化疏水基团含量以及铜与镓的比例来进一步提高催化性能. 通过X射线衍射、氢气程序升温还原、X射线光电子能谱和CO吸附红外光谱等方法进行表征, 结果表明, 镓物种对铜纳米颗粒的电子结构进行了调控, 提升了催化剂上Cu^δ⁺物种的含量, 从而抑制了逆水煤气转换反应, 实现了CO选择性的降低. 此外, 水蒸气等温吸附、水蒸气程序升温脱附和水滴接触角测试等结果表明, 引入疏水甲基基团可以调控催化剂表面的浸润性, 提升水分子的扩散速率并抑制其二次吸附. 在镓改性和甲基基团疏水修饰的协同作用下, Cu/Ga-SiO₂-20Me催化剂上CO₂转化率从5.5%提升至9.7%, DME选择性达到59.3%, 而CO选择性则从40%降至11.3%. 在100 h的长周期测试中, 表现出较好的催化稳定性. 通过研究CO₂加氢催化剂(Cu/SiO₂-20Me)和甲醇脱水催化剂(Ga/SiO₂-20Me)的混合方式, 探讨了疏水环境下铜和镓物种之间的协同作用. 结果表明, 镓改性和疏水基团的协同作用有助于串联反应的同步进行, 避免了甲醇中间体的气相扩散和二次吸附. 对于物理混合催化剂, 由于两种活性金属存在一定的空间距离, 导致铜基催化剂上生成的甲醇必须气相扩散并二次吸附于镓催化剂表面以进行后续甲醇脱水生成二甲醚反应. 然而, 在疏水甲基基团的作用下, 抑制了极性甲醇分子的二次吸附, 导致了二甲醚选择性的降低. 尽管如此, 对于Cu/Ga-SiO₂-20Me复合催化剂, 铜与镓物种的毗邻性实现了CO₂加氢制甲醇和甲醇脱水制二甲醚串联反应能够同步进行, 成功避免了甲醇中间体的气相扩散和二次吸附. 此外, 疏水甲基基团可以加速反应生成水的扩散, 促进反应平衡正向进行, 实现高效催化.

综上, 本文研究结果为催化系统的空间分布控制提供了有益的见解, 并为设计适用于疏水催化过程的新型串联催化剂提供了参考. 此外, 该理念为催化剂体系的设计提供了新的思路.

关键词: CO₂加氢, 铜催化剂, 疏水性调节, 镓助剂, 催化剂稳定性

Abstract:

Supported Cu catalysts are widely studied for the hydrogenation of CO₂ to dimethyl ether (DME). However, they suffer from insufficient durability and DME selectivity. Herein, we overcome these issues by modulating the gallium species and hydrophobic methyl groups to obtain a silica-supported copper catalyst, achieving a Cu/Ga-SiO₂-Me catalyst with significantly improved DME selectivity and catalyst durability. Characterizations of the catalysts showed that the gallium species electronically modulated the Cu nanoparticles, resulting in abundant Cu^δ⁺ species in the catalyst, which minimized the reverse water-gas shift reaction and thus reduced CO selectivity. In addition, the methyl groups contributed to the rapid removal of water from the catalyst surface, which hindered Cu sintering and accelerated catalysis. Consequently, the Cu/Ga-SiO₂-20Me exhibited a CO₂ conversion of 9.7%, selectivities of DME and methanol of 59.3% and 28.4%, and CO selectivity of only 11.3%. The strategy used in this study may provide rational guidance for improving current industrial catalysts.

Key words: Hydrogenation of CO₂, Copper catalyst, Hydrophobic modulation, Gallium promoter, Catalyst stability

李航杰, 肖月华, 肖佳乐, 范凯, 李炳宽, 李晓龙, 王亮, 肖丰收. 镓改性的铜基疏水催化剂用于CO₂选择性加氢制二甲醚的研究[J]. 催化学报, 2023, 54: 178-187.

Hangjie Li, Yuehua Xiao, Jiale Xiao, Kai Fan, Bingkuan Li, Xiaolong Li, Liang Wang, Feng-Shou Xiao. Selective hydrogenation of CO₂ into dimethyl ether over hydrophobic and gallium-modified copper catalysts[J]. Chinese Journal of Catalysis, 2023, 54: 178-187.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(23)64535-8

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图/表 7

Fig. 1. XRD patterns (A), Nitrogen sorption isotherms (B), and H2-TPR profiles (C). Note: In this manuscript, the Cu/Ga-SiO2 and Cu/Ga-SiO2-20Me catalysts imply the samples with a Ga/Cu molar ratio of 1.0 unless something else is mentioned.

Fig. 2. SEM images of Cu/SiO2 (a) and Cu/Ga-SiO2-20Me (b). TEM images of Cu/SiO2 (c) and Cu/Ga-SiO2-20Me (d).

Fig. 3. In situ XPS-AES spectra of Cu/SiO2 (A), Cu/Ga-SiO2 (B), and Cu/Ga-SiO2-20Me (C). In situ CO adsorption DRIFTS of Cu/SiO2 (D), Cu/Ga-SiO2 (E), and Cu/Ga-SiO2-20Me (F).

Fig. 4. (A) Data showing the performances of different catalysts in the hydrogenation of CO2 to DME. (B) Data summarizing the DME selectivity as a function of CO2 conversion in the previous tests. (C) Data showing the catalytic performances of Cu/Ga-SiO2-20Me in the hydrogenation of CO2 to DME under different reaction temperatures. Reaction conditions: 6000 mL gcat-1 h-1, 3 MPa, 240 °C, Ar/CO2/H2 volume ratio of 4/24/72. (D) Durability evaluation of the Cu/Ga-SiO2-20Me catalyst in the hydrogenation of CO2. Reaction conditions: 6000 mL gcat-1 h-1, 3 MPa, 240 °C, Ar/CO2/H2 volume ratio of 4/24/72, and TOS at 100 h.

Fig. 5. In situ DRIFTS of Cu/SiO2 (A), Cu/Ga-SiO2 (B), and Cu/Ga-SiO2-20Me (C) in a flow of Ar/CO2/H2 (4/24/72, vol%) at 240 °C. Water adsorption isotherms (D) and water-TPD profiles (E) of different catalysts. (F) Water droplet contact angles of different catalysts.

Fig. 6. (A) MS profiles showing the CH4 signal by evaluating the Cu/SiO2-20Me and Cu/Ga-SiO2-20Me catalysts in contact with 10 vol% H2/Ar at 300 °C. (B) Water-desorption profiles of the spent Cu/SiO2 and Cu/Ga-SiO2-20Me catalysts. (C) Water droplet contact angle of spent Cu/Ga-SiO2-20Me catalyst. (D) TG-DSC profiles of the spent Cu/Ga-SiO2-20Me catalyst.

Fig. 7. Data showing the catalytic performances of Cu/Gax-SiO2-yMe catalysts with various contents of gallium (A) and methyl groups (B). Reaction conditions: 6000 mL gcat-1 h-1, 3 MPa, 240 °C, Ar/CO2/H2 volume ratio of 4/24/72. (C) Catalytic performance of the physically mixed Cu/SiO2-20Me and Ga/SiO2-20Me catalysts with various mixing manners and Cu/Ga-SiO2-20Me catalyst in the hydrogenation of CO2 to DME. Reaction conditions: 6000 mL gcat-1 h-1, 3 MPa, 240 °C, Ar/CO2/H2 volume ratio of 4/24/72. (D) Scheme showing the diffusion of intermediates over the physically mixed Cu/SiO2-20Me with Ga/SiO2-20Me catalyst and bifunctional Cu/Ga-SiO2-20Me catalyst in the hydrogenation of CO2 to DME.

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镓改性的铜基疏水催化剂用于CO₂选择性加氢制二甲醚的研究

Selective hydrogenation of CO₂ into dimethyl ether over hydrophobic and gallium-modified copper catalysts

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