CN107899595B - CoP/石墨烯气凝胶高效析氢复合材料及制备方法 - Google Patents
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Abstract
本发明属于电解水的催化剂，特指CoP/石墨烯气凝胶高效析氢复合材料及制备方法及其析氢性能的研究。该方法通过简单的溶胶凝胶法制得水凝胶，再通过高温磷化的方法获得CoP/石墨烯气凝胶高效析氢复合材料。本发明制备的CoP/石墨烯气凝胶高效析氢复合材料具有优异的电催化析氢性能。
Description
技术领域
本发明属于电解水的催化剂，特指CoP/石墨烯气凝胶高效析氢复合材料及制备方法及其析氢性能的研究。
背景技术
这些年，能源危机问题被越来越多的研究工作者关注，当前开发和利用清洁有效的能源是解决目前危机的重要挑战之一。从能源清洁及可循环的角度考虑，氢能作为一种高效、清洁、环保的二次能源具有资源丰富，热值高，环保无污染，利用形式多样等特点，已被普遍认为是一种理想的可替代化石燃料的新能源，有着无可比拟的巨大优势和无限广阔的应用前景。然而如何通过有效的途径获得较为廉价的氢能源，是目前科研工作者研究的主要内容之一，地球上水资源丰富，通过水的电解获得氢气是有效的途径之一，但是水的电解能源转化效率低是制约其工业化生产的因素之一，因此设计和开发高性能，低成本的电解水的催化剂具有极其重要的意义。
近几年，过渡金属硫化物，磷化物在能源存储及在电催化中的潜在应用得到了研究工作者的广泛关注。过渡金属Co、Ni、Fe、Mo基硫化物、氮化物、磷化物是一类重要的HER催化剂，对MEx(M:Fe、Co、Ni；E:S、N、P)一系列硫化物催化析氢性能研究表明，在酸性电解液中，CoS2、NiS2、CoP、NiP等具有较好的电化学析氢性能。最近，磷化物在电化学析氢方面具有优越的电催化性能，其中CoP作为磷化物中的佼佼者，日益被研究者关注。天然多糖基气凝胶作为纳米粒子构成的三维网络结构的新型材料，因其具有典型的多孔网络结构、高比表面积、高孔隙率、低密度、低热导率、低介电常数、高吸附性能等特点，且因其骨架和孔隙的纳米尺度化所引起的尺寸效应、表面效应和宏观量子隧道效应，在力学、热学、光学等众多领域有着广泛的应用。海藻酸钠做为天然多糖中的一种，由于其良好的生物降解性和生物相容性，被广泛用于制药、化工、生物、食品等领域。海藻酸钠溶液与金属阳离子鳌合，形成的气凝胶，在治理环境污染，降解有机物方面被广泛报道，但在电化学析氢方面鲜有报道。本发明较为新颖的通过海藻酸钠溶液和金属Co的鳌合作用，形成海藻酸盐水凝胶，冷冻干燥后进一步高温磷化形成磷化钴气凝胶，通过加入氧化石墨烯，进一步改善其电子传导速率，最终形成磷化钴石墨烯气凝胶，极大地的提高了其电化学催化性能。
发明内容
本发明旨在提供CoP/石墨烯气凝胶高效析氢复合材料的制备方法，该方法通过简单的溶胶凝胶法制得水凝胶，再通过高温磷化的方法获得CoP/石墨烯气凝胶高效析氢复合材料。本发明制备的CoP/石墨烯气凝胶高效析氢复合材料具有优异的电催化析氢性能。
CoP/石墨烯气凝胶高效析氢复合材料的制备方法，具体包括以下步骤：
(1)称取Co(NO3)2.6H2O溶解到去离子水中搅拌，形成质量分数为2.5wt％的Co(NO3)2.6H2O溶液A。
(2)称取海藻酸钠(SA)加入到去离子水中搅拌形成质量分数为1wt％的均一的海藻酸钠溶液B。
(3)量取不同量的GO溶液注入溶液B中，搅拌，在超声仪中超声，得到分散液C。
(4)在常温下将分散液C注入到溶液A中，形成水凝胶，形成的水凝胶陈化后用去离子水和乙醇分别浸泡，洗涤。
(5)将陈化，浸泡，洗涤过后的水凝胶在冷冻干燥机中冷冻干燥直至形成干凝胶。
(6)分别取干凝胶和红磷，红磷置于管式炉上游位置，加入GO形成的干凝胶置于下游，进行高温磷化，最终得到含有不同质量分数石墨烯的CoP石墨烯气凝胶。
步骤(3)中，GO的质量分数以mGO/mGO+mSA计算为分别为5wt％-20wt％；优选5wt％，GO溶液的浓度为2mg/ml。
步骤(4)中，所述溶液A和分散液C的体积比是1:1；陈化时间为12h。
步骤(4)中，浸泡3次，洗涤3次，每次浸泡时间为2h。
步骤(5)中，冷冻干燥时间为48h。
步骤(6)中，所述干凝胶和红磷的质量比为1:1；红磷的质量要小于1g，红磷的质量越大，高温越易出现事故；高温磷化温度区间为700-900℃，磷化时间为4h，通氮气作为保护气，升温速率2-8℃/min。
本发明的有益效果为：
(1)本发明制备的CoP/石墨烯气凝胶高效析氢复合材料,较为新颖的将多糖钴基气凝胶通过高温磷化合成，其制备工艺简单,成本低,易于大规模工业化生产，该材料具有良好的电化学稳定性和析氢性能，在解决环境污染和能源危机方面有良好的应用前景。
(2)电化学体系中高的比表面积和良好的导电性对催化剂好坏起着至关重要的作用，海藻酸钠基气凝胶具有发达的网络孔洞结构，将CoP负载在石墨烯气凝胶上，极大的增大了催化剂的比表面积，发达的网络结构对CoP的固定和分散也起到了很好的作用，从而增加了催化剂与电解液的有效接触面积，增大催化剂的活性位点，提高析氢性能。CoP/石墨烯气凝胶高效析氢复合材料，塔菲尔斜率57mV dec-1，电流密度为10mA/cm2时的过电位为120mV；与其他文献单体磷化钴在析氢方面相比较性能有了明显的提高。
(3)CoP/石墨烯气凝胶高效析氢复合材料可作为性能优良的电化学析氢催化剂。GAs结构具有良好的亲水性，可以使电解液接触更多的石墨烯边缘和表面，石墨烯优良的电导率极大的促进电荷的传输，有效地提升了复合后催化剂的稳定性。因此，CoP/石墨烯气凝胶高效析氢复合材料显著地提升了催化剂对电解水析氢性能，在电催化实际应用领域具有广阔的前景。
附图说明
图1为实施例1所制备的样品的XRD图谱，与CoP/As、CoP/GAs-5、CoP/GAs-10、CoP/GAs-20的XRD图的对比图；说明我们已经成功合成了磷化钴负载的石墨烯气凝胶。
图2为实施例1所制备CoP/GAs-5的样品在不同倍率下的透射电镜图，(a)图是标尺为0.2um条件下透射电镜图，(b)图是标尺为100nm条件下透射电镜图；说明磷化钴很好的负载在石墨烯气凝胶基底上。
图3为实施例1所制备的CoP/石墨烯气凝胶高效析氢复合材料在酸性溶液中电化学析氢效果图；说明合成的CoP/石墨烯气凝胶复合材料具有高效的析氢性能。
具体实施方式
下面结合说明书附图具体实施例对本发明作进一步说明。
实施例1：
制备CoP/气凝胶(CoP/As)高效析氢复合材料
(1)称取Co(NO3)2.6H2O溶解到去离子水中搅拌，形成质量分数为2.5wt％的Co(NO3)2.6H2O溶液A。
(2)称取海藻酸钠(SA)倒入到去离子水中搅拌12h形成质量分数为1wt％的均一的海藻酸钠溶液B。
(3)在常温下将50ml的溶液B注入到50ml溶液A中，形成水凝胶。形成的水凝胶陈化12小时，然后用去离子水和乙醇分别浸泡，每次2h，洗涤3次。
(4)将陈化，浸泡，洗涤过后的水凝胶在冷冻干燥机中冷冻干燥48小时,形成干凝胶。
(5)分别取干凝胶和红磷(P)，红磷置于管式炉上游位置，干凝胶置于下游，进行高温磷化，磷化温度为800℃，最终得到CoP/As。
实施例2：
制备CoP/石墨烯气凝胶高效析氢复合材料
(1)称取Co(NO3)2.6H2O溶解到去离子水中搅拌，形成质量分数为2.5wt％的Co(NO3)2.6H2O溶液A。
(2)称取海藻酸钠(SA)倒入到去离子水中搅拌12h形成质量分数为1wt％的均一的海藻酸钠溶液B。
(3)分别量取质量分数为5％、10％和20％的GO(2mg/ml)溶液注入溶液B中，搅拌，在超声仪中超声，得到分散液C；
(4)在常温下将50ml的分散C注入到50ml的溶液A中，形成水凝胶。形成的水凝胶陈化12小时，然后用去离子水和乙醇分别浸泡3次，每次2h，洗涤3次。
(5)将陈化，浸泡，洗涤过后的水凝胶在冷冻干燥机中冷冻干燥48小时，直至形成干凝胶。
(6)分别取干凝胶和红磷(P),红磷置于管式炉上游位置，不同质量分数GO形成的干凝胶置于下游，进行高温磷化，磷化温度为800℃，最终得到含有不同质量分数石墨烯的CoP石墨烯气凝胶，分别命名为CoP/GAs-5，CoP/GAs-10和CoP/GAs-20。
Claims (7)
1.CoP/石墨烯气凝胶高效析氢复合材料，其特征在于，采用如下方法制备：
(1)称取Co(NO3)2.6H2O溶解到去离子水中搅拌，形成质量分数为2.5wt％的Co(NO3)2.6H2O溶液A；
(2)称取海藻酸钠(SA)加入到去离子水中搅拌形成质量分数为1wt％的均一的海藻酸钠溶液B；
(3)量取不同量的GO溶液注入溶液B中，搅拌，在超声仪中超声，得到分散液C；
(4)在常温下将分散液C注入到溶液A中，形成水凝胶，形成的水凝胶陈化后用去离子水和乙醇分别浸泡，洗涤；
(5)将陈化，浸泡，洗涤过后的水凝胶在冷冻干燥机中冷冻干燥直至形成干凝胶；
(6)分别取干凝胶和红磷，红磷置于管式炉上游位置，加入GO形成的干凝胶置于下游，进行高温磷化，最终得到含有不同质量分数石墨烯的CoP石墨烯气凝胶。
2.如权利要求1所述的CoP/石墨烯气凝胶高效析氢复合材料，其特征在于，步骤(3)中，GO的质量分数以mGO/mGO+mSA计算为分别为5wt％-20wt％；GO溶液的浓度为2mg/ml。
3.如权利要求2所述的CoP/石墨烯气凝胶高效析氢复合材料，其特征在于，GO的质量分数以mGO/mGO+mSA计算为分别为5wt％。
4.如权利要求1所述的CoP/石墨烯气凝胶高效析氢复合材料，其特征在于，步骤(4)中，所述溶液A和分散液C的体积比是1:1；陈化时间为12h。
5.如权利要求1所述的CoP/石墨烯气凝胶高效析氢复合材料，其特征在于，步骤(4)中，浸泡3次，洗涤3次，每次浸泡时间为2h。
6.如权利要求1所述的CoP/石墨烯气凝胶高效析氢复合材料，其特征在于，步骤(5)中，冷冻干燥时间为48h。
7.如权利要求1所述的CoP/石墨烯气凝胶高效析氢复合材料，其特征在于，步骤(6)中，所述干凝胶和红磷的质量比为1:1；红磷的质量要小于1g，红磷的质量越大，高温越易出现事故；高温磷化温度区间为700-900℃，磷化时间为4h，通氮气作为保护气，升温速率2-8℃/min。
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