CN106694003A - 一种双金属磷化物析氢催化剂及制备方法 - Google Patents
一种双金属磷化物析氢催化剂及制备方法 Download PDFInfo
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Abstract
本发明公开了一种双金属磷化物析氢催化剂及制备方法。该催化剂由磷掺杂纳米碳和双金属磷化物纳米颗粒组成。其制备方法包括：首先将金属氯化盐溶液与有机磷源溶液混合制备前驱体；再将前驱体高温分解制备双金属磷化物析氢催化剂。本发明制备成本低廉，方法简便，易于放大，电化学催化活性较高。
Description
技术领域
本发明属于电催化制氢技术领域，具体涉及一种双金属磷化物析氢催化剂及制备方法。
背景技术
催化制氢具有效率高、能耗低以及环境友好等优点，是极具应用前景的制氢技术。但是由于目前存在严重的阴极极化问题，大大增加了催化制氢技术的能耗，从而提高了制氢成本。Pt等贵金属以及它们的合金具有最好的电催化氢气析出性能，但是它们的成本高，难以大规模应用。发展高性能低成本的非贵金属催化剂对推动电催化制氢技术的应用具有重要意义。
过渡金属(Fe、Co、Ni、Mn)磷化物具有成本低廉，析氢催化活性优异以及制备方式多样等优点，近年得到迅速发展。但是目前所制备的金属磷化物在析氢过程中稳定性不好。此外，金属磷化物在生产过程中常采用次磷酸钠作为无机磷源，次磷酸钠加热后容易产生磷化氢等有毒气体，危害环境，并且次磷酸钠具有强还原性，对设备要求极高，不利于磷化物的进一步应用。
发明内容
本发明的目的在于提供一种双金属磷化物析氢催化剂及制备方法，克服现有技术缺陷。本发明的原料成本低廉，制备方法简便，易于放大，并且采用有机磷源，避免了磷化氢等有毒气体的释放，对设备要求也有所降低。
本发明的目的通过以下技术方案来实现：
一种双金属磷化物析氢催化剂，它由原位生成的磷掺杂的纳米碳和双金属磷化物纳米颗粒组成，在碱性电解液中具有较好的析氢催化活性。
本发明的一种双金属磷化物析氢催化剂的制备方法是按下列步骤进行：
(1)称取一定比例的两种金属氯化盐中加入40mL无水乙醇，室温下搅拌至溶解；
(2)取一定量的沉淀剂溶于60mL无水乙醇，室温下进行搅拌至溶解；
(3)将步骤(1)中制得的澄清金属氯化盐溶液缓慢滴加进步骤(2)制备的澄清溶液中，并充分搅拌，搅拌时间为1.5～2h；
(4)对步骤(3)制得的沉淀采用无水乙醇进行洗涤，并干燥；
(5)将步骤(4)制得的干燥沉淀充分研磨，并在一定温度下进行煅烧；
(6)对步骤(5)制得的产物采用无水乙醇洗涤并干燥，得到双金属磷化物析氢催化剂。
所述步骤(1)中加入的两种金属氯化为盐为Ni、Fe、Co等金属的氯化盐中的任意两种，其摩尔比为0～8。
所述步骤(2)中沉淀剂为三苯基氧膦(OPPh3)，并且与金属盐总量摩尔比为0.5～4。
所述步骤(4)中制得的沉淀为M1M2-OPPh3前驱体，其中，M1和M2代表上述所涉及的两种金属，具体包括Co-OPPh3、Fe-OPPh3、NiFe-OPPh3、NiCo-OPPh3、CoFe-OPPh3。
所述步骤(5)的升温速率为2～10℃/min，所用保护气为氮气，流量为30mL/min，煅烧温度为450～650℃。
本发明方法有如下特点：
1、本发明的制备方法简便，原料成本低廉，易于放大，采用三苯基氧膦(OPPh3)等有机磷源，避免了次磷酸钠等无机磷源的使用，减少了次磷酸钠分解产生磷化氢气体的环境危害，以及次磷酸钠强还原性带来的设备损耗。
2、利用OPPh3作为两种金属离子的共沉淀剂，可以在最后制得的电催化剂中有效结合两种金属。两种金属磷化物之间存在协同作用，从而能更有效的促进氢气析出反应。
3、OPPh3中含有磷和碳两种元素，其中磷元素在煅烧过程中用来形成具有分解水催化活性的双金属磷化物；而碳主要以苯环结构存在，经高温处理可形成原位生成的碳。经高温煅烧制备的双金属磷化物结构独特，同时碳材料增加了电荷转移能力，进而增强纳米复合电催化剂催化析氢的能力。
附图说明
图1是本发明专利析氢反应活性测试图
具体实施方式
实施例1
称取2.43g CoCl2置于40mL无水乙醇中，室温下搅拌至金属盐溶解成均匀溶液A；称取5.62g三苯基氧膦(OPPh3)置于60mL无水乙醇中，室温下搅拌至溶解形成无色澄清溶液B；将溶液A缓慢滴加进入溶液B，并连续搅拌2h，得到沉淀，采用无水乙醇洗涤并干燥，即得Co-OPPh3前驱体。
将Co-OPPh3前驱体充分研磨，并称取0.5g置于管式炉中，在氮气环境下，2℃/min升温至600℃，保温2h；将所得产物采用无水乙醇反复洗涤并干燥，制得CoPx/PC电催化剂(PC为磷掺杂的碳材料)。
本实施例所制备的CoPx/PC催化剂在溶剂中分散性较好，在碱性条件下，电流密度为10mA/cm2时，析氢过电压为0.546V。
实施例2
称取2.73g FeCl3置于40mL无水乙醇中，室温下搅拌至金属盐溶解成均匀溶液A；称取5.62g三苯基氧膦(OPPh3)置于60mL无水乙醇中，室温下搅拌至溶解形成无色澄清溶液B；将溶液A缓慢滴加进入溶液B，并连续搅拌2h，得到沉淀，采用无水乙醇洗涤并干燥，即得Fe-OPPh3前驱体。
将Fe-OPPh3前驱体充分研磨，并称取0.5g置于管式炉中，在氮气环境下，2℃/min升温至600℃，保温2h；将所得产物采用无水乙醇反复洗涤并干燥，制得FePx/PC电催化剂。
本实施例所制备的FePx/PC催化剂在溶剂中分散性较好，在碱性条件下，电流密度为10mA/cm2时，析氢过电压为0.659V。
实施例3
分别称取1.21g NiCl2和1.37g FeCl3置于40mL无水乙醇中，室温下搅拌至金属盐溶解成均匀溶液A；称取5.62g三苯基氧膦(OPPh3)置于60mL无水乙醇中，室温下搅拌至溶解形成无色澄清溶液B；将溶液A缓慢滴加进入溶液B，并连续搅拌2h，得到沉淀，采用无水乙醇洗涤并干燥，即得NiFe-OPPh3前驱体。
将NiFe-OPPh3前驱体充分研磨，并称取0.5g置于管式炉中，在氮气环境下，2℃/min升温至600℃，保温2h；将所得产物采用无水乙醇反复洗涤并干燥，制得NiFePx/PC电催化剂。
本实施例所制备的NiFePx/PC催化剂在溶剂中分散性较好，在碱性条件下，电流密度为10mA/cm2时，析氢过电压为0.648V。
实施例4
分别称取1.21g NiCl2和1.21g CoCl2置于40mL无水乙醇中，室温下搅拌至金属盐溶解成均匀溶液A；称取5.62g三苯基氧膦(OPPh3)置于60mL无水乙醇中，室温下搅拌至溶解形成无色澄清溶液B；将溶液A缓慢滴加进入溶液B，并连续搅拌2h，得到沉淀，采用无水乙醇洗涤并干燥，即得NiCo-OPPh3前驱体。
将NiCo-OPPh3前驱体充分研磨，并称取0.5g置于管式炉中，在氮气环境下，2℃/min升温至600℃，保温2h；将所得产物采用无水乙醇反复洗涤并干燥，制得NiCoPx/PC电催化剂。
本实施例所制备的NiCoPx/PC催化剂在溶剂中分散性较好，在碱性条件下，电流密度为10mA/cm2时，析氢过电压为0.421V。
实施例5
分别称取1.21g CoCl2和1.37g FeCl3置于40mL无水乙醇中，室温下搅拌至金属盐溶解成均匀溶液A；称取5.62g三苯基氧膦(OPPh3)置于60mL无水乙醇中，室温下搅拌至溶解形成无色澄清溶液B；将溶液A缓慢滴加进入溶液B，并连续搅拌2h，得到沉淀，采用无水乙醇洗涤并干燥，即得CoFe-OPPh3前驱体。
将CoFe-OPPh3前驱体充分研磨，并称取0.5g置于管式炉中，在氮气环境下，2℃/min升温至600℃，保温2h；将所得产物采用无水乙醇反复洗涤并干燥，制得CoFePx/PC电催化剂。
本实施例所制备的CoFePx/PC催化剂在溶剂中分散性较好，在碱性条件下，电流密度为10mA/cm2时，析氢过电压为0.450V。
Claims (6)
1.一种双金属磷化物析氢催化剂，其特征在于，催化剂由磷掺杂的纳米碳和双金属磷化物纳米颗粒组成。
2.根据权利要求1，其特征在于，催化剂按照以下步骤制备：
(1)将两种金属氯化盐加入无水乙醇中，搅拌至溶解；
(2)取沉淀剂溶于无水乙醇，搅拌至溶解；
(3)将步骤(1)制得的溶液缓慢加入步骤(2)制得的溶液中，充分搅拌；
(4)将步骤(3)制得的沉淀采用无水乙醇洗涤，并干燥；
(5)将步骤(4)得到的沉淀充分研磨，并在一定温度下煅烧；
(6)对步骤(5)煅烧制得的产物洗涤并干燥，得到双金属磷化物析氢催化剂。
3.根据权利要求1和2，其特征在于，所述的金属盐为Ni、Fe、Co等金属的氯化盐中的任意两种。
4.根据权利要求2，其特征在于，步骤(1)所述的两种金属盐摩尔比为0～8。
5.根据权利要求2，其特征在于，步骤(2)所述的中沉淀剂为三苯基氧膦(OPPh3)，沉淀剂与金属氯化盐总量摩尔比为0.5～4。
6.根据权利要求2，其特征在于，所述步骤(6)的升温速率为2～10℃/min，所用保护气为氮气，流量为30mL/min，煅烧温度为450～650℃。
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