(廊坊師范學院 化學與材料科學學院，廊坊 065000)
摘 要: 通過液相自組裝合成沸石咪唑酯型金屬有機骨架ZIF-67，將ZIF-67與次亞磷酸鈉均勻混合后經氣相磷化處理制得納米磷化鈷催化劑，并用于催化硼氫化鈉水解制氫。考察不同混合比例對催化劑成分及性能的影響，探究堿性硼氫化鈉溶液組成與反應溫度對催化劑性能的影響。采用場發(fā)射掃描電鏡(FE-SEM)、能譜儀(EDS)、X射線衍射(XRD)、比表面積分析(BET)對材料進行表征。結果表明：當ZIF-67與次亞磷酸鈉按質量比1:4反應時所得納米Co2P催化劑性能最佳；該催化劑最適反應液組成為4% NaBH4-8% NaOH(質量分數)，產氫速率高達4.95 L/(min·g) (25 ℃)；表觀活化能為64.2 kJ/mol。與文獻同類催化劑相比，所制備納米Co2P催化劑對NaBH4水解制氫具有更高的催化活性。
關鍵字: 磷化鈷；ZIF-67；氣相磷化；硼氫化鈉；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
