Sulfidation and selenidation of nickel nanoparticles
Sulfidation and selenidation of nickel nanoparticles
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DOI：
10.1002/cey2.83
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发表时间：
2021-08-01
期刊：
影响因子：
20.5
通讯作者：
Tracy, Joseph B.
中科院分区：
文献类型：
--
作者：
Lynch, Brian B.;Kelliher, Andrew P.;Tracy, Joseph B.
过渡金属硫属化物纳米颗粒（NP）对于能量应用（包括电池、超级电容器和电催化）是令人感兴趣的。已经建立了许多合成Ni NP的方法，并且从模板Ni NP形成Ni氧化物和磷化物的转化化学是众所周知的。然而，镍纳米颗粒的硫化和硒化的研究要少得多。我们报道了一种使用元素硫、1-十六硫醇、硫脲、三辛基硫化膦、元素硒和硒代亚硒酸钠将Ni模板纳米颗粒转化为硫化物和硒化物产物纳米颗粒的方法。当硫/硒前驱体与镍的摩尔比为2 mmol时，得到了Ni 3S 2、Ni 9 S8、NiS、NiSO 4、Ni 3S 4、Ni 3Se 2和NiSe等相的产物。产品在相互扩散过程中通过Kirkendall效应形成空隙。已经确定了与前体的化学性质和产物的相有关的趋势。虽然一些前体含有磷，但在任何产物中均没有显著的磷掺入。硫化和硒化过程中NP尺寸的增加与成熟一致。镍硫化物和硒化物纳米颗粒作为析氢反应的电催化剂的应用也得到了证实。
Transition metal chalcogenide nanoparticles (NPs) are of interest for energy applications, including batteries, supercapacitors, and electrocatalysis. Many methods have been established for synthesizing Ni NPs, and conversion chemistry to form Ni oxide and phosphides from template Ni NPs is well-understood. Sulfidation and selenidation of Ni NPs have been much less explored, however. We report a method for the conversion of Ni template NPs into sulfide and selenide product NPs using elemental sulfur, 1-hexadecanthiol, thiourea, trioctylphosphine sulfide, elemental selenium, and selenourea. While maintaining mole ratios of 2 mmol sulfur/selenium precursor: mmol Ni, products with phases of Ni3S2, Ni9S8, NiS, NiSO4 center dot 6H(2)O, Ni3S4, Ni3Se2, and NiSe have been obtained. The products have voids that form through the Kirkendall effect during interdiffusion. Trends relating the chemical properties of the precursors to the phases of the products have been identified. While some precursors contained phosphorus, there was no significant incorporation of phosphorus in any of the products. An increase of the NP size during sulfidation and selenidation is consistent with ripening. The application of Ni sulfide and selenide NPs as electrocatalysts for the hydrogen evolution reaction is also demonstrated.