(廊坊师范学院 化学与材料科学学院，廊坊 065000)
摘 要: 通过液相自组装合成沸石咪唑酯型金属有机骨架ZIF-67，将ZIF-67与次亚磷酸钠均匀混合后经气相磷化处理制得纳米磷化钴催化剂，并用于催化硼氢化钠水解制氢。考察不同混合比例对催化剂成分及性能的影响，探究碱性硼氢化钠溶液组成与反应温度对催化剂性能的影响。采用场发射扫描电镜(FE-SEM)、能谱仪(EDS)、X射线衍射(XRD)、比表面积分析(BET)对材料进行表征。结果表明：当ZIF-67与次亚磷酸钠按质量比1:4反应时所得纳米Co2P催化剂性能最佳；该催化剂最适反应液组成为4% NaBH4-8% NaOH(质量分数)，产氢速率高达4.95 L/(min·g) (25 ℃)；表观活化能为64.2 kJ/mol。与文献同类催化剂相比，所制备纳米Co2P催化剂对NaBH4水解制氢具有更高的催化活性。
关键字: 磷化钴；ZIF-67；气相磷化；硼氢化钠；催化水解
（College of Chemistry and Materials Science, Langfang Normal University, Langfang 065000, China）
Abstract:Zeolitic imidazolate framework of ZIF-67 was synthesized by self-assembly process. For catalytic hydrolysis of sodium borohydride (NaBH4), cobalt phosphides nanocatalysts were prepared from the mixture of ZIF-67 and sodium hypophosphite (NaH2PO2) by solid-state phosphorization treatment. In this work, effects of the mass ratio of ZIF-67 and NaH2PO2 on catalyst component and performance were investigated; moreover, influences of alkaline NaBH4 solution component and reaction temperature on catalyst performance were studied. For material characterization, field-emission scanning electron microscopy (FE-SEM), energy dispersive spectroscopy (EDS), X-ray diffraction (XRD) and specific surface area analysis (BET) were conducted. Experimental results indicate that optimal ratio of ZIF-67 and NaH2PO2 is 1:4, resulting in a highly efficient Co2P nanocatalyst. It is found that the optimal solution component are 4% NaBH4-8% NaOH (mass fraction), giving a hydrogen generation rate up to 4.95 L/(min·g) (25 ℃) and apparent activation energy of 64.2 kJ/mol. Compared with similar catalysts in literature, the prepared Co2P nanocatalyst presents much higher activity for sodium borohydride hydrolysis to generate hydrogen.
Key words: cobalt phosphide; ZIF-67; vapor phase phosphorization; sodium borohydride; catalytic hydrolysis
