钙钛矿型甲醇水蒸气重整制氢催化材料的研究

doi:10.6023/A20080374

摘要/Abstract

采用溶胶凝胶法合成了钙钛矿复合氧化物, 负载氧化铜后得钙钛矿负载型催化材料, 通过XRD (X射线衍射分析)、BET(比表面积测试)、H₂-TPR(程序升温还原分析)、XPS (X射线光电子能谱)等手段对催化材料进行了表征, 考察了不同种类钙钛矿负载纳米铜催化材料的结构、性质对甲醇水蒸气重整制氢性能的影响. 结果显示, 钙钛矿负载纳米铜催化材料的催化活性主要与催化剂的铜比表面积、表面晶格氧缺位以及活性组分和载体间的相互作用有关. 其中, CuO/LaCrO₃钙钛矿负载型催化材料的表面氧空穴含量较多, 活性组分与载体间相互作用较强, 因此催化甲醇水蒸气重整制氢活性较好. 当反应温度为360 ℃时, CuO/LaCrO₃钙钛矿型催化剂并未出现明显失活现象, 甲醇转化率为98.6%, 产氢速率为694.9 mL•kg_cat ^–1•s ^–1.

关键词: 钙钛矿, 氧化铜, 催化剂, 甲醇水蒸气重整, 氢气

As an important clean energy, hydrogen energy has the advantages of light weight, high calorific value, and environmental protection. If hydrogen energy can be well developed and stored, it will play more and more important roles in the human production and life. Methanol steam reforming (MSR) hydrogen production technology, which has been used in industry for many years, is the best choice for methanol hydrogen production because of its high hydrogen content in reforming tail gas and mature technology. ABO₃ perovskite oxide is a new type of material. Compared with other materials, due to its unique electronic structure, it has various properties such as electricity, magnetism, optics and chemistry. It have shown great application prospects in many fields. The perovskite composite oxide was synthesized by the sol-gel method. After loading copper oxide, a perovskite-supported catalytic material was obtained. The catalytic material was characterized by XRD (X-ray diffraction), BET (Brunner-Emmet-Teller), H₂-TPR (H₂-temperature programmed reduction) and XPS (X-ray photo- electron spectra). The effect of the structure and properties of perovskite-loaded nano-copper catalytic materials on the performance of methanol steam reforming for hydrogen production were investigated. The results showed that the catalytic activity of the perovskite-loaded nano-copper catalytic material is mainly related to the copper surface area, the catalytic and reductive properties, the oxygen lattice deficiency on the surface of the catalyst, and the interaction between the active component and the carrier. Among them, because the CuO/LaCrO₃ perovskite-supported catalytic materials have the larger copper surface area, the lower reduction temperature, the more oxygen vacancies on the surface, and the stronger interaction between the active component, the catalytic activity of methanol steam reforming for hydrogen production is better than that of the CuO/LaNiO₃, CuO/LaFeO₃ and CuO/La₂Zr₂O₇. When the reaction temperature was 360 ℃, the CuO/LaCrO₃ perovskite catalyst did not show significant deactivation, the methanol conversion rate was 98.6%, and the hydrogen production rate was 694.9 mL•kg_cat ^–1•s ^–1.

Key words: perovskite, CuO, catalyst, steam reforming of methanol, hydrogen

引用此文

肖国鹏, 乔韦军, 张磊, 庆绍军, 张财顺, 高志贤. 钙钛矿型甲醇水蒸气重整制氢催化材料的研究[J]. 化学学报, 2021, 79(1): 100-107.

Guopeng Xiao, Weijun Qiao, Lei Zhang, Shaojun Qing, Caishun Zhang, Zhixian Gao. Study on Hydrogen Production Catalytic Materials for Perovskite Methanol Steam Reforming[J]. Acta Chimica Sinica, 2021, 79(1): 100-107.

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图/表 15

图1. 钙钛矿型催化材料的XRD谱图

Figure 1. XRD patterns of perovskite catalytic material a—LaCrO3; b—LaNiO3; c—LaFeO3; d—La2Zr2O7

图2. CuO/LaBO3(B=Cr、Ni、Fe)和CuO/La2Zr2O7催化剂XRD谱图

Figure 2. XRD patterns of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

催化剂	比表面积/ (m ²•g ^–1)	孔容/ (cm ³•g ^–1)	孔径/nm
LaCrO ₃	10.6	0.02	3.06
LaNiO ₃	7.4	0.02	3.06
LaFeO ₃	10.8	0.02	3.41
La ₂Zr ₂O ₇	4.0	0.01	3.31

表1. 载体具有的物化性质

Table 1. The physical and chemical properties of the carrier

催化剂	比表面积/ (m ²•g ^–1)	孔容/ (cm ³•g ^–1)	孔径/nm	铜比表面积/ (m ²•g _cat ^–1)	产氢速率 ^a / (mL•kg _cat ^–1• s ^–1)
CuO/ LaCrO ₃	12.1	0.03	3.06	2.1	665.5
CuO/ LaNiO ₃	7.5	0.02	3.03	1.2	427.7
CuO/ LaFeO ₃	11.5	0.03	3.86	1.1	276.6
CuO/ La ₂Zr ₂O ₇	4.1	0.01	3.48	1.1	304.3

表2. 催化材料物化性质及其催化MSR反应的产氢速率

Table 2. The catalyst physicochemical properties and hydrogen production rate in the MSR reaction

图3. CuO/LaBO3(B=Cr、Ni、Fe)和CuO/La2Zr2O7催化剂的H2-TPR谱图

Figure 3. H2-TPR profiles of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

图4. CuO/LaBO3(B=Cr、Ni、Fe)和CuO/La2Zr2O7催化剂的La 3d的XPS谱图

Figure 4. XPS spectra of La 3d for CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

图5. CuO/LaBO3(B=Cr、Ni、Fe)和CuO/La2Zr2O7催化剂的Cu 2p的XPS谱图

Figure 5. XPS spectra of Cu 2p for CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

图6. CuO/LaBO3(B=Cr、Ni、Fe)和CuO/La2Zr2O7催化剂的Cu俄歇谱图

Figure 6. Cu Auger spectra of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

催化剂	Cu ⁺/(Cu ⁺+Cu ²⁺) (at%)
CuO/LaCrO ₃	56
CuO/LaNiO ₃	51
CuO/LaFeO ₃	48
CuO/La ₂Zr ₂O ₇	48

表3. CuO/LaBO3(B=Cr、Ni、Fe)和CuO/La2Zr2O7催化剂各自对应的铜俄歇谱XPS曲线拟合结果

Table 3. Cu LMM XPS curve fitting results of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts

图7. CuO/LaBO3(B=Cr、Ni、Fe)和CuO/La2Zr2O7催化剂的O 1s 的XPS 谱图

Figure 7. XPS spectra of O 1s of CuO/LaBO3(B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

催化剂	O _ads/(O _latt+O _ads+O _H2O) (at%)
CuO/LaCrO ₃	34
CuO/LaNiO ₃	31
CuO/LaFeO ₃	28
CuO/La ₂Zr ₂O ₇	27

表4. CuO/LaBO3(B=Cr、Ni、Fe)和CuO/La2Zr2O7催化剂的O 1s XPS曲线拟合结果

Table 4. Curve fitting results of CuO/LaBO3 (B=Cr, Ni, Fe) and CuO/La2Zr2O7 catalysts and O 1s XPS curves

图8. 反应温度对催化活性的影响

Figure 8. The influence of the reaction temperature on the catalytic activity Reaction conditions: atmospheric, GHSV=800 h–1,V(Water)∶V(Methanol)=1.2∶1, no carrier gas. a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

图9. 反应温度对CO摩尔分数的影响

Figure 9. The influence of the reaction temperature on the CO molar content Reaction conditions: atmospheric, GHSV=800 h–1,V(Water)∶V(Methanol)=1.2∶1, no carrier gas. a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

图10. 反应温度对氢气选择性的影响

Figure 10. The influence of the reaction temperature on the Hydrogen selectivity Reaction conditions: atmospheric, GHSV=800 h–1,V(Water)∶V(Methanol)=1.2∶1, no carrier gas. a—CuO/LaCrO3; b—CuO/LaNiO3; c—CuO/LaFeO3; d—CuO/La2Zr2O7

图11. CuO/LaCrO3催化剂的稳定性

Figure 11. Stability test of the CuO/LaCrO3 catalyst Reaction conditions: atmospheric,T=320 ℃, GHSV=800 h–1,V(Water)∶V(Methanol)=1.2∶1, no carrier gas

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