Controlling the growth of activated carbon supported nickel phosphide catalysts via adjustment of surface group distribution for hydrodeoxygenation of palmitic acid
Controlling the growth of activated carbon supported nickel phosphide catalysts via adjustment of surface group distribution for hydrodeoxygenation of palmitic acid
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DOI：
10.1016/j.cattod.2018.03.051
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发表时间：
2019-01
期刊：
影响因子：
5.3
通讯作者：
Hui Xin;Wenjun Zhou;Keyao Zhou;Xiangze Du;Dan Li;Changwei Hu
中科院分区：
文献类型：
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作者：
Hui Xin;Wenjun Zhou;Keyao Zhou;Xiangze Du;Dan Li;Changwei Hu
磷化镍是一种很有前途的贵金属催化剂替代品。传统的控制磷化镍物种（包括Ni 2P、Ni 3P和Ni 12 P5）生长的方法是调节Ni/P摩尔比或改变载体。在这里，我们报告了一种新的方法来控制磷化镍物种的生长，通过调整活性炭表面含氧基团的类型。用HNO3预处理活性炭，可显著提高活性炭中单键O、单键C、双键O基团的含量。在活性炭负载磷化镍催化剂的制备过程中，单键O单键C双键O基团可能与P相互作用形成P单键O单键C双键O基团。在低温下，生成的P单键O单键C双键O抑制了P物种的还原，从而抑制了磷化镍的生成;而在873 K还原时，促进了活性炭上纯Ni2P的生成。经NH3·H2O处理后的活性炭表面-OH基团含量增加，有利于1/1比例的Ni2P和Ni12P5的同时生成，且该催化剂对棕榈酸具有良好的催化加氢脱氧活性。我们的研究结果表明，如何简单的碱和酸预处理可以用来调整界面基团分布，从而提供了一个策略，以合理地设计过渡金属磷化物负载催化剂。
Nickel phosphides were known to be promising substitute for noble metal used in various catalysts. The traditional method of controlling the growth of nickel phosphide species, including Ni2P, Ni3P, and Ni12P5, was either modulating Ni/P molar ratio or changing support. Here, we report a new method to control the growth of nickel phosphide species by tuning the types of surface oxygenated group types on activated carbon. The pretreatment of activated carbon with HNO3remarkably increased the content of single bondOsingle bondCdouble bondO groups. In the preparation process of activated carbon supported nickel phosphide catalyst, the single bondOsingle bondCdouble bondO groups might interact with P to form Psingle bondOsingle bondCdouble bondO groups. The formed Psingle bondOsingle bondCdouble bondO inhibited the reduction of P species at low temperature, and thus inhibited the formation of the nickel phosphides; whereas at 873 K reduction, the formation of pure Ni2P on activated carbon was enhanced. However, the content of -OH groups content increased on activated carbon treated by NH3∙H2O, which might be favorable for the simultaneous formation of Ni2P and Ni12P5with 1/1 ratio, and the thus formed catalyst displayed excellent catalytic hydrodeoxygenation activity for palmitic acid. Our results demonstrated how simple base and acid pretreatment could be used to tune the interfacial group distribution, hereby providing a strategy to rationally design transition metal phosphide supported catalysts.