负载型Co-Ni-Cr-P/γ-Al2O3催化剂的制备及其制氢性能研究

张月, 颜双, 孙凯利, 王桂雪, 谢广文

表面技术 ›› 2017, Vol. 46 ›› Issue (12) : 179-185.

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表面技术 ›› 2017, Vol. 46 ›› Issue (12) : 179-185. DOI: 10.16490/j.cnki.issn.1001-3660.2017.12.029
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负载型Co-Ni-Cr-P/γ-Al2O3催化剂的制备及其制氢性能研究

  • 张月, 颜双, 孙凯利, 王桂雪, 谢广文
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Preparation and Hydrogen Production Property of Supported Co-Ni-Cr-P/γ-Al2O3 Catalysts

  • ZHANG Yue, YAN Shuang, SUN Kai-li, WANG Gui-xue, XIE Guang-wen
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摘要

目的 优化Co-Ni-Cr-P合金催化剂镀液配方,探究其催化碱性NaBH4溶液制备氢气的最佳条件。方法 利用化学镀的方法,在三氧化二铝(γ-Al2O3)基体表面镀覆了Co-Ni-Cr-P合金。利用X射线衍射仪(XRD)、场发射扫描电子显微镜(FE-SEM)、X射线能量色散谱仪(EDS)、化学吸附仪(BET)和电感耦合等离子体发射光谱(ICP),对该催化剂的结构、微观形貌等进行了系统表征。结果 Co-Ni-Cr-P合金镀层均匀地分布在三氧化二铝载体表面,ICP测得该催化剂的相对组成为48.46%Co+ 19.77%Ni+ 21.02%Cr+10.75%P(质量分数)。化学镀Co-Ni-Cr-P的实验参数为:21.96 g/L硫酸钴,2.44 g/L硫酸镍,0.6 g/L硝酸铬,20 g/L柠檬酸钠,10 g/L氟化铵,40 g/L次亚磷酸钠,pH=9,温度(90±1) ℃。结论 20 mL含4%的硼氢化钠溶液在40 ℃时的产氢速率约为1500 mL/(g?min)。根据动力学计算可得,Co-Ni-Cr-P/γ-Al2O3合金催化剂催化碱性NaBH4溶液制备氢气的反应活化能为45.96 kJ/mol。

Abstract

The work aims to study optimum conditions of generating hydrogen by catalyzing alkaline NaBH4 solution by optimizing formula of Co-Ni-Cr-P alloy catalysts. The Co-Ni-Cr-P alloy was coated on the surface of aluminium sesquioxide (γ-Al2O3) in the method of electroless deposition. Structure and microstructure of the Co-Ni-Cr-P/γ-Al2O3 catalysts were characterized systematically with X-ray diffractometer (XRD), field emission scanning electron microscope (FE-SEM), X-ray energy dispersive spectrometer (EDS), nitrogen adsorption-desorption isotherm (BET) and inductively coupled plasma atomic emission spectrometer (ICP). Co-Ni-Cr-P alloy coating was well distributed onto the surface of carrier γ-Al2O3. According to ICP results, relative composition was 48.46wt% Co, 19.77wt% Ni, 21.02wt% Cr and 10.75wt% P (mass fraction, similarly hereinafter). Experiment parameters of electrolessly plating Co-Ni-Cr-P were: 21.96 g/L cobalt sulfate heptahydrate, 2.44 g/L nickel sulfate hexahydrate, 0.6 g/L Chromic nitrate nonahydrate, 20 g/L sodium citrate dehydrate, 10 g/L ammonium fluoride, 40 g/L sodium hypophosphite Monohydrate, pH=9 and temperature (90±1) ℃. Average hydrogen generation rate of 20 mL 4% NaBH4 solution was 1500 mL/(g?min). Reaction activation energy of the Co-Ni-Cr-P/γ-Al2O3 alloy catalysts in hydrogen generation was measured to be 45.96 kJ/mol.

关键词

催化剂;化学镀;γ-Al2O3基体;硼氢化钠;制氢;Co-Ni-Cr-P合金

Key words

catalyst; electroless plating; γ-Al2O3 substrate; sodium borohydride; hydrogen generation; Co-Ni-Cr-P alloy

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张月, 颜双, 孙凯利, 王桂雪, 谢广文. 负载型Co-Ni-Cr-P/γ-Al2O3催化剂的制备及其制氢性能研究[J]. 表面技术. 2017, 46(12): 179-185
ZHANG Yue, YAN Shuang, SUN Kai-li, WANG Gui-xue, XIE Guang-wen. Preparation and Hydrogen Production Property of Supported Co-Ni-Cr-P/γ-Al2O3 Catalysts[J]. Surface Technology. 2017, 46(12): 179-185

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