CN113967480A - 一种磷掺杂二硫化钼/多孔碳复合材料的制备方法及其应用 - Google Patents
一种磷掺杂二硫化钼/多孔碳复合材料的制备方法及其应用 Download PDFInfo
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- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 45
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 43
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- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 13
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 12
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
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Abstract
本发明公开了一种用于电解水制氢的由天然琼脂衍生的多孔碳/磷掺杂二硫化钼复合材料，催化剂具有二硫化钼与多孔碳基质复合的分级结构，制备具有高分散性，形貌可控。本发明优点在于使用天然琼脂作为碳源，即在提供一种新型的生物原料的利用方式，工艺简单；通过杂原子掺杂，引起二硫化钼结构缺陷，来提高材料的整体导电性。本发明的催化剂在酸性条件下表现出优异的电解水析氢催化活性，有望代替现阶段使用的铂基等贵金属电解水析氢催化剂。
Description
技术领域
本发明涉及一种由琼脂衍生的多孔碳/磷掺杂二硫化钼复合材料的制备方法，属于电极材料技术领域，主要应用于电催化析氢反应、钠离子电池及超级电容器等电极材料中。
背景技术
能源供应主要依靠化石燃料，这给我们的社会造成了严重的副作用，例如空气污染和全球变暖。因此，开发清洁和可再生的替代本地能源迫切需要满足社会需求并克服环境问题。其中氢被认为是有效的清洁和可再生能源，因为它可以通过分解水来生产。在水分解过程中，需要有效的催化剂来驱动氢释放反应(HER)。尽管铂(Pt)和Pt基合金对氢气析出反应(HER)表现出最高的电催化活性，但其高成本和少量地壳含量极大地阻碍了它们的实际实现。因此，开发大量、稳定、高效的HER电催化剂是当今面向清洁能源社会未来的广泛科学技术研究的主题。
二硫化钼是一种典型的过渡金属硫化物，具有与石墨烯类似的层状结构。二硫化钼独特的结构和物理化学性质使其在催化、润滑、电子探针、电极材料等领域中有着较广泛的应用。二硫化钼作为加氢、脱硫催化剂，不仅具有较高的催化活性，而且具有较高的抗硫、抗中毒性能。然而，目前二硫化钼基催化剂仍存在一定的问题：(1)基面无活性，只有边缘具有电催化活性，需要增大活性表面积；(2)本征催化活性位点较少，需要引入更多的缺陷或其他活性位点；(3)本征导电性较差，需要导电载体支持。因此，提高二硫化钼电化学性能最好的办法就是引入碳作为基底，来扩大表面积提供更多的活性位点。近来，N、B、S、P等杂原子掺杂由于优异的物理和化学性能吸引了研究者们大量的关注。特别是对于磷原子，因为磷的电负性低，共价半径更大，从而引起结构缺陷。
经检索发现如下几篇公开的专利及文献：
CN 201711476596.2该发明所述二硫化钼/多孔碳纳米球复合材料以多孔氮掺杂的碳球为核，以二硫化钼为壳层的核壳式结构，复合球的直径在500-600nm之间，二硫化钼均匀的包覆在多孔氮掺杂的碳球表面，且呈花瓣状。该发明虽然增大了比表面积，但其合成过程过于繁琐且实验条件较苛刻，难以大规模生产。
CN202010503056.4该发明公开了一种功能化改性二硫化钼纳米片的制备方法，首先通过球磨法将六氯环三磷腈和盐酸胍与给定量的二硫化钼粉末均匀混合后，将前驱物放入石英炉中煅烧制备磷掺杂纳米片，最后以原位生长方式将硼化钴纳米片修饰在二硫化钼纳米片表面.从而获得功能化改性二硫化钼纳米片。该发明提供的功能化改性二硫化钼纳米片制备方法简单、成本低，但磷源原材料在煅烧过程中存在安全隐患。
经分析，现有的磷掺杂二硫化钼复合多孔碳制备方法还有待改进。
本专利提出一种磷掺杂二硫化钼/多孔碳复合材料的制备方法。天然琼脂是红海藻中的一种多糖，具有丰富的物质资源，无毒，可生物降解，相容性等。琼脂经过碳化处理，得到一种二硫化钼定向生长在氮掺杂多孔碳上的复合材料。并且，本发明还将磷酸二氢钠引入该体系，磷原子的电负性低，共价半径更大，从而引起二硫化钼的结构产生缺陷，进一步提高整体的导电性。
发明内容
本发明的目的在于克服现有技术不足，提供一种过程简单，绿色无污染，合成产率较高，新颖的制备方法。
本发明采用的技术方案是：
一种用于制备如权利要求1的复合催化剂的制备方法，步骤如下：
(1)以天然琼脂粉作为碳源，尿素作为氮源制备多孔碳材料；
(2)取1g的琼脂粉，溶解在20mL的去离子水中，在80～95℃水浴锅中加热并持续搅拌至其溶解，再取1g氢氧化钾和1g尿素分散在上述溶液中，搅拌至溶解；
(3)将其放入100℃烘箱内干燥7h；
(4)干燥后的材料置于管式炉内，在N2的气氛下以5℃/min的速率升温至750℃，保持2h后缓慢降至室温；
(5)将获得的粉末用稀盐酸、去离子水交替混合洗涤数次，最终将碳在100℃下干燥8h，制得氮掺杂的多孔碳材料；
(6)取6mg氮掺杂的多孔碳材料于30mL去离子水中搅拌30min；
(7)取钼酸钠与硫代乙酰胺比例为1∶6溶解在(6)中，将混合物超声处理30min，再加入0.1、0.2、0.3g磷酸二氢钠；
(8)转移到50mL衬有特氟龙的不锈钢高压釜中，并在200℃下保持24h。高压釜自然冷却至室温后，收集最终产物，分别用乙醇和水洗涤，在真空烘箱中于80℃干燥12h，经研磨处理后得到磷掺杂二硫化钼/多孔碳复合电极材料。
本发明的优点和积极效果为：
本发明的催化剂的原料来源广泛，均为成熟工业品，成本低廉；该催化剂在酸性条件下表现出优异的电解水析氢催化活性，有望代替现阶段使用的铂基等贵金属电解水析氢催化剂。碳材料具有多孔结构，可以使得活性表面充分暴露，电解液充分浸润，有利于氢气及时脱附；杂原子掺杂可以使二硫化钼的结构产生缺陷，进一步提高整体的导电性。本发明提供的制备方法过程简单，绿色无污染，合成产率较高。作为电催化材料用于电催化析氢反应、锂离子电池及超级电容器等电极材料中等。
附图说明
图1是本发明二硫化钼和磷掺杂二硫化钼/多孔碳复合材料的扫描电镜照片；
图2是本发明磷掺杂二硫化钼/多孔碳复合材料不同掺杂量的电催化析氢性能图。
具体实施方式
下面通过具体实施例对本发明作进一步详述，以下实施例只是描述性的，不是限定性的，不能以此限定本发明的保护范围。
实施例1
(1)以天然琼脂粉作为碳源，尿素作为氮源制备多孔碳材料；取1g的琼脂粉，溶解在20mL的去离子水中，在90℃水浴锅中加热并持续搅拌至其溶解，再取1g氢氧化钾和1g尿素分散在上述溶液中，搅拌至溶解；将其放入80℃烘箱内干燥7h；干燥后的材料置于管式炉内，在N2的气氛下以5℃/min的速率升温至750℃，保持2h后缓慢降至室温；将获得的粉末用稀盐酸和去离子水交替洗涤数次，最终将碳在100℃下干燥8h，制得氮掺杂的多孔碳材料；取6mg的氮掺杂的多孔碳材料于30mL去离子水中搅拌30min；取钼酸钠与硫代乙酰胺比例为1∶6溶解在上述溶液中，将混合物超声处理30min，再加入0.05g磷酸二氢钠。转移到50mL衬有特氟龙的不锈钢高压釜中，并在200℃下保持24h。高压釜自然冷却至室温后，收集最终产物；分别用乙醇和水洗涤；在真空烘箱中于80℃干燥12h后得到磷掺杂二硫化钼/多孔碳复合电极材料。
(2)所制备的一种由天然琼脂衍生的多孔碳/磷掺杂二硫化钼复合材料按照以下步骤进行电化学测试：
(3)称取以上催化剂5mg，将其分散在包含有490μL去离子水，490μL乙醇溶液，20μLNafion溶液(5％)的混合液中，超声30min以上，形成均匀悬浮液。然后取上述悬浮液5μL，滴涂在直径为3毫米的玻碳电极上，自然干燥即可制备得到工作电极。
(4)电化学测试采用标准的三电极体系，在CH1760E电化学工作站(上海辰华仪器公司)上进行相应的性能测试。酸性条件使用0.5mol/L H2SO4电解液，其中，以铂丝作为对电极，饱和甘汞电极(SCE)为酸性电解液中的参比电极，工作电极为上述所制备玻碳电极。所有的测试均在室温下进行，线性扫描伏安曲线范围从0.1～-0.4V，扫描速率为5mV/s。极化曲线的实验数据均进行iR校正，并且电极电势换算成可逆氢电极电势(RHE)，换算方程如下：
(5)酸性条件下，E(RHE)＝E(SCE)+0.241+0.059pH；
(6)Tafel曲线由LSV曲线转换得到，以log(|j|)为横坐标，以E(RHE)为纵坐标，将曲线线性部分拟合，得到Tafel斜率。
(7)该发明制备的催化剂在酸性条件下表现出了优异的电催化析氢活性，如图2所示，电流密度为-10mA/cm2时的过电位仅为210mV，Tafel斜率为54mV/dec。
实施例2
(1)以天然琼脂粉作为碳源，尿素作为氮源制备多孔碳材料；取1g的琼脂粉，溶解在20mL的去离子水中，在90℃水浴锅中加热并持续搅拌至其溶解，再取1g氢氧化钾和1g尿素分散在上述溶液中，搅拌至溶解；将其放入80℃烘箱内干燥7h；干燥后的材料置于管式炉内，在N2的气氛下以5℃/min的速率升温至750℃，保持2h后缓慢降至室温；将获得的粉末用稀盐酸和去离子水交替洗涤数次，最终将碳在100℃下干燥8h，制得氮掺杂的多孔碳材料；取6mg的氮掺杂的多孔碳材料于30mL去离子水中搅拌30min；取钼酸钠与硫代乙酰胺比例为1∶6溶解在上述溶液中，将混合物超声处理30min，再加入0.1g磷酸二氢钠。转移到50mL衬有特氟龙的不锈钢高压釜中，并在200℃下保持24h。高压釜自然冷却至室温后，收集最终产物；分别用乙醇和水洗涤；在真空烘箱中于80℃干燥12h后得到磷掺杂二硫化钼/多孔碳复合电极材料。
(2)上述催化剂如图2所示，在电流密度为-10mA/cm2时的过电位为167mV，Tafel斜率为45mV/dec。
实施例3
(1)以天然琼脂粉作为碳源，尿素作为氮源制备多孔碳材料；取1g的琼脂粉，溶解在20mL的却离子水中，在90℃水浴锅中加热并持续搅拌至其溶解，再取1g氢氧化钾和1g尿素分散在上述溶液中，搅拌至溶解；将其放入80℃烘箱内干燥7h；干燥后的材料置于管式炉内，在N2的气氛下以5℃/min的速率升温至750℃，保持2h后缓慢降至室温；将获得的粉末用稀盐酸和去离子水交替洗涤数次，最终将碳在100℃下干燥8h，制得氮掺杂的多孔碳材料；取6mg的氮掺杂的多孔碳材料于30mL去离子水中搅拌30min；取钼酸钠与硫代乙酰胺比例为1∶6溶解在上述溶液中，将混合物超声处理30min，再加入0.2g磷酸二氢钠。转移到50mL衬有特氟龙的不锈钢高压釜中，并在200℃下保持24h。高压釜自然冷却至室温后，收集最终产物；分别用乙醇和水洗涤；在真空烘箱中于80℃干燥12h后得到磷掺杂二硫化钼/多孔碳复合电极材料。
(2)上述催化剂如图2所示，在电流密度为-10mA/cm2时的过电位为190mV，Tafel斜率为50mV/dec。
综上所述，本发明制备的一种由天然琼脂衍生的多孔碳/磷掺杂二硫化钼复合材料方法简单，可控，可放大，原料绿色环保无污染。本发明利用琼脂在惰性气氛下进行煅烧后进行水热，在水热过程中引入磷源、钼源和硫源，得到具有分级结构的二硫化钼。通过调节磷掺杂量，可得到不同电化学性能的磷掺杂二硫化钼/氮掺杂碳材料。
以上详细描述了本发明的较佳具体实施例。但本领域的技术人员可以理解：在不脱离本发明及所附权利要求的精神和范围内，各种替换、变化和修改都是可能的，因此，本发明的范围不局限于实施例所公开的内容。
Claims (8)
1.一种磷掺杂二硫化钼/多孔碳复合材料制备方法，其特征在于：首先以多孔碳为基底，通过水热法在氮掺杂碳基底上制备了磷掺杂的二硫化钼纳米片。具体制备方法包括以下步骤：
(1)以天然琼脂粉作为碳源、尿素作为氮源，氢氧化钾作为活化剂，将氢氧化钾、尿素和琼脂粉按照1∶1∶1比例混合溶解在20mL的去离子水中，在80～95℃水浴锅中加热并持续搅拌至其溶解。然后再将其放入80～100℃烘箱内干燥7h。干燥后的材料置于管式炉内，在N2的气氛下以5℃/min的速率升温至750℃，保持2h后缓慢降至室温。将获得的纳米粉末用稀盐酸、去离子水交替混合洗涤数次，最终将碳在100℃下干燥8h，制得氮掺杂的多孔碳材料；
(2)取6mg步骤(1)得到的氮掺杂的多孔碳材料于30mL去离子水中搅拌30min。以钼酸钠作为钼源、硫代乙酰胺作为硫源。将钼酸钠∶硫代乙酰胺按照1∶6的摩尔比溶解在上述溶液中。然后将混合物超声处理30min后，再加入0.1、0.2、0.3g磷酸二氢钠来控制磷的量。将其转移到50mL衬有特氟龙的不锈钢高压釜中，并在200℃下保持24h。高压釜自然冷却至室温后，收集最终产物，分别用乙醇和水洗涤，最后在真空烘箱中于80℃干燥12h。经研磨处理后得到磷掺杂二硫化钼/多孔碳复合电极材料。
2.根据权利要求1所述的磷掺杂二硫化钼/多孔碳复合电极的制备方法，其特征在于，所述的碳材料是以天然琼脂作为碳源。
3.根据权利要求1所述的磷掺杂二硫化钼/多孔碳复合电极的制备方法，其特征在于，步骤(1)中，以氢氧化钾作为活化剂，在达到一定温度时时，KOH完全反应，以钾单质存在并在碳上产生微孔。
4.根据权利要求1所述的磷掺杂二硫化钼/多孔碳复合电极的制备方法，其特征在于，步骤(1)中，以尿素作为氮源，分解成氨气，氨气是一种既能产生孔又能在碳表面引入氮的化学物质。
5.根据权利要求1所述的磷掺杂二硫化钼/多孔碳复合电极的制备方法，其特征在于，步骤(2)中，将钼酸钠∶硫代乙酰胺按照1∶6的摩尔比溶解在上述溶液中。再加入0.1、0.2、0.3g磷酸二氢钠来探究磷掺杂量。
6.根据权利要求1所述的磷掺杂二硫化钼/多孔碳复合电极的制备方法，其特征在于，步骤(2)中，反应时间的控制，置于50mL衬有特氟龙的不锈钢高压釜中，并在200℃下保持24h。
7.一种根据权利要求1所述的方法制备了磷掺杂二硫化钼/多孔碳复合材料。
8.一种根据权利要求1所述磷掺杂二硫化钼/多孔碳复合材料在电催化析氢领域的应用。
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