Low temperature light-assisted hydrogen production from aqueous reforming ethylene glycol over Pt/Al2O3 and Pd/Al2O3 catalysts
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摘要: 采用浸渍还原法制备了氧化铝负载的Pt和Pd纳米颗粒催化剂，用于光辅助乙二醇水相重整制氢反应。结果表明，光照能够有效降低乙二醇水相重整制氢的活化能，Pt/Al2O3比Pd/Al2O3具有更高的H2转换频率（TOF）和更低的CO选择性。采用XRD、TEM、UV-vis等技术对催化剂的结构和形貌进行了表征，原位漫反射红外光谱（DRIFTS）表明，光照能促进乙二醇分子O-H键的断裂。理论计算表明，Pt/Al2O3催化乙二醇重整制氢反应产物中较低的CO选择性主要归因于CO在Pt表面较小的反应能垒，能够较快与H2O解离的O反应生成CO2。Abstract: Al2O3 supported Pt and Pd nanoparticle catalysts were prepared by impregnation-reduction method, and employed in the photocatalytic aqueous-phase reforming of ethylene glycol. Light illumination can decrease the reaction activation energy remarkably. Pt/Al2O3 exhibits much higher H2 turnover frequency (TOF) and lower CO selectivity than Pd/Al2O3 catalyst. Their morphology and structure were characterized by XRD, TEM, UV-vis techniques. In situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) indicates light can promote the cleavage of O-H bonds of ethylene glycol molecule. DFT calculation suggests the lower CO selectivity over Pt/Al2O3 catalyst can be attributed to the low energy barriers of reaction in the step of CO+O→CO2.
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Key words:
- hydrogen production /
- ethylene glycol /
- photocatalysis /
- aqueous-phase reforming /
- metal catalyst
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图 1 生物醇水相重整制氢反应路径示意图[4]
Figure 1 Reaction pathways of H2 production by aqueous-phase reforming of biomass-derived alcohols
图 2 (a) Pt/Al2O3催化剂的TEM照片; (b) Pd/Al2O3催化剂的TEM照片; (c) Pt和Pd的粒径分布; (d) Pt/Al2O3、Pd/Al2O3和Al2O3的XRD谱图
Figure 2 (a) TEM image of Pt/Al2O3; (b) TEM image of Pd/Al2O3; (c) particle size distribution of Pt and Pd nanoparticle; (d) XRD patterns of Pt/Al2O3, Pd/Al2O3 and Al2O3
图 3 (a) Pt/Al2O3、Pd/Al2O3和Al2O3的UV-vis谱图; (b)乙二醇水溶液的UV-vis谱图和高压汞灯的输出光谱谱图
Figure 3 (a) UV-vis spectra of Pt/Al2O3, Pd/Al2O3 and Al2O3; (b) UV-vis spectra of ethylene glycol solution and high pressure Hg light
图 4 不同温度下光照对(a) Pt/Al2O3和(c) Pd/Al2O3光助催化乙二醇水相重整制氢催化性能的影响; 不同光强对(b) Pt/Al2O3和(d) Pd/Al2O3光助催化乙二醇水相重整制氢催化性能的影响
Figure 4 Effect of temperature on catalytic performance in ethylene glycol aqueous phase reforming over (a) Pt/Al2O3 and (c) Pd/Al2O3; effect of light intensity on catalytic performance in ethylene glycol aqueous phase reforming over (b) Pt/Al2O3 and (d) Pd/Al2O3 reaction condition: ethylene glycol 2mL, H2O 18mL, catalyst 50mg, 3h, the light intensity for (a) and (c) is 0.1W/cm2, the reaction temperature of (b) and (d) is 150℃
图 5 (a) Pt/Al2O3和(b) Pd/Al2O3催化乙二醇水相重整制氢光暗反应的阿伦尼乌斯曲线
Figure 5 Arrhenius plots for (a) Pt/Al2O3 and (b) Pd/Al2O3 catalysts in ethylene glycol aqueous phase reforming reaction with or without light
图 6 光照对Pt/Al2O3 (a)和Pd/Al2O3 (b)催化乙二醇水相重整制氢气相产物选择性的影响
Figure 6 Effect of light on the gas products selectivity of ethylene glycol aqueous phase reforming reaction over Pt/Al2O3 (a) and Pd/Al2O3 (b)catalysts
图 7 不同温度下(a)暗反应和(b)紫外光照射乙二醇在Pt/Al2O3催化剂上吸附的红外漫反射光谱谱图
Figure 7 DRIFTS spectra for the adsorption of ethylene glycol in the dark (a) and under UV light irradiation (b) at different temperatures over Pt/Al2O3
表 1 Pt/Al2O3和Pd/Al2O3催化光暗活性对比
Table 1 Catalytic performance of Pt/Al2O3 and Pd/Al2O3 with or without light
Entry Catalyst TOF /h-1 Selectivity of gas products s/% Selectivity of liquid products s/% H2 CO CH4 CO2 ethanol aldehyde 1 Pt/Al2O3 dark 197.9 67.0 0.1 0.4 32.5 72.1 27.9 2 Pt/Al2O3 light 1152.5 71.2 0.3 2.3 26.2 64.7 35.3 3a Pt/Al2O3 dark - - - - - - - 4a Pt/Al2O3 light - - - - - - - 5b - dark - - - - - - - 6b - light - - - - - - - 7 Pd/Al2O3 dark 11.0 66.7 13.8 0.6 18.9 95.3 4.7 8 Pd/Al2O3 light 120.5 65.4 24.4 3.5 6.7 89.6 10.4 9a Pd/Al2O3 dark - - - - - - - 10a Pd/Al2O3 light - - - - - - - reaction conditions: ethylene glycol 2mL, H2O 18mL, catalyst 50mg, 150℃, 3h, the light intensity for 0.1W/cm2 for light reaction; a: without ethylene glycol; b: without catalyst 
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表 2 Pt(111)和Pd(111)面上不同基元步骤上计算的反应能垒(Eb)和反应能(ΔE)
Table 2 Calculated energy barriers of reaction (Eb), reaction energies (ΔE) of the elementary steps on Pt(111), Pd(111) surfaces
Elementary step Pd(111) Pt(111) Eb/eV ΔE/eV Eb/eV ΔE/eV R1 H2O$ \to $H+OH 1.42 -0.02 2.07 0.73 R2 OH$ \to $H+O 1.34 0.15 1.29 0.06 R3 OH+OH$ \to $O+H2O 0.83 -0.42 0.58 -0.60 R4 H+H$ \to $H2 1.85 1.07 1.50 0.64 R5 CO+O$ \to $ CO2 1.97 -0.35 1.47 -0.91
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