CN113546642B - 纳米Ag修饰海胆状多孔碱式碳酸钴复合材料及其制法 - Google Patents

纳米Ag修饰海胆状多孔碱式碳酸钴复合材料及其制法 Download PDF

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CN113546642B
CN113546642B CN202010341136.4A CN202010341136A CN113546642B CN 113546642 B CN113546642 B CN 113546642B CN 202010341136 A CN202010341136 A CN 202010341136A CN 113546642 B CN113546642 B CN 113546642B
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吴兴才
王伟
陶友荣
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Nanjing University
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Abstract

该发明专利的名称为：“纳米Ag修饰海胆状多孔碱式碳酸钴复合材料及其制法”。具体地说，是用纳米Ag为晶种，以硝酸亚钴(等可溶性亚钴盐)、尿素等为原料，水乙醇联合溶剂热合成纳米Ag修饰海胆状多孔碱式碳酸钴纳米复合材料。它为Ag纳米颗粒(20‑25nm)锚固在多孔CCHH纳米棒上(直径大约25‑80nm，长2‑3微米)，这些纳米棒构成海胆状的微球(直径约5微米)。这种材料是一种很好的碱性条件下电解水的阳极催化剂，性能超过商用RuO2，价格低廉，稳定性好，具有很好的应用前景。本发明公开了这种材料及其制法。

Description

纳米Ag修饰海胆状多孔碱式碳酸钴复合材料及其制法
技术领域
本发明涉及纳米Ag修饰海胆状多孔碱式碳酸钴复合材料及其制法。具体地说，是用纳米Ag为晶种水热合成纳米Ag修饰海胆状多孔碱式碳酸钴纳米复合材料。
背景技术
为了解决能源与环境问题，人们提出电解水获得氢气和氧气的方案，这是一个非常有前途的方案，但由于阳极吸氧过电位高和缓慢的动力学阻碍其发展。目前公认的最好的析氧电催化剂是RuO2和IrO2，由于它们是低丰度的贵金属使实际应用受到限制，因此，开发高效低值的催化剂势在必行。碱式碳酸钴(Co(CO3)0.5OH·0.11H2O，简写为CCHH)作为前驱体常常在不同的气氛中分解为钴的化合物[参见：(a)L.Zhu，Z.Wen，W.Mei，Y.Li，Z.Ye，J.Phys.Chem.C 2013，117，20465-20473.(b)A Y.Wang，H.Xia，L.Lu，J.Lin，ACS Nano2010，4，1425-1432.(c)X.Yang，K.Fan，Y.Zhu，J.Shen，X.Jiang，P.Zhao，S.Luan，C.Li，ACSAppl.Mater.Interfaces 2013，5，997-1002.]。作为析氧反应(OER)催化剂只有少数几篇研究。例如：CCHH生长在碳布上作为OER催化剂在10mA/cm2的电流密度下，过电位是509mV[参见：Y.Wang，W.Ding，S.G.Chen，Y.Nie，K.Xiong，Z.D.Wei，Chem.Commun.2014，50，15529-15532.]；CCHH生长在碳纳米管上作为OER催化剂在10mA/cm2的电流密度下，过电位是466mV[参见：Y.Zhang，B.Cui，O.Derr，Z.Yao，Z.Qin，X.Deng，J.Li，H.Lin，Nanoscale 2014，6，3376-3383.]；CCHH多孔纳米纸锚固在多壁碳纳米管上在1M KOH溶液中，在10mA/cm2的电流密度下，过电位是285mV[参见：Y.X.Zhang，Q.Q.Xiao，X.Guo，X.X.Zhang，Y.F.Xue，L.Jing，X.Zhai，Y.M.Yan，K.N.Sun，J.Power Sources 2015，278，464-472.]。到目前为止，并没有纳米Ag修饰海胆状多孔CCHH复合材料的报道。在这里，用纳米Ag为晶种水热合成纳米Ag修饰的多孔海胆状碱式碳酸钴纳米复合材料(Ag和多孔CCHH的摩尔比为0.0261)，在1M KOH溶液中，经电催化析氧反应(OER)测试，在10mA/cm2的电流密度下的过电位是273mV，性能优于RuO2；经20次循环伏安激发后，在10mA/cm2的电流密度下的过电位是268mV，并且有很好的稳定性。因此，在电催化分解水方面有很好的应用前景。
发明内容
本发明的目的是纳米Ag修饰海胆状多孔碱式碳酸钴复合材料及其制备方法。
本发明的技术方案如下：
一种纳米Ag修饰海胆状多孔碱式碳酸钴复合材料，它为Ag(20-25nm)颗粒锚固在多孔CCHH纳米棒(直径大约25-80nm，长2-3微米)上，这些纳米棒构成海胆状的微球(直径约5微米)。
一种制备上述复合材料的方法，它是纳米Ag悬浊液，加入Co(NO3)2·6H2O和尿素、水、乙醇混合溶液，在120℃下水热反应1-3小时，经离心、洗涤、干燥获得产品。
本发明的复合材料经XRD测定，峰的位置与强度与Ag和CCHH相匹配。因表明产品的纯度比较高。通过SEM照片和高分辨电镜观察，为由多孔CCHH纳米棒构成的海胆结构，Ag锚固在多孔CCHH纳米棒上，纳米棒直径约20-80nm、长度约为2-3微米。
从OER性能可以看出，该复合材料具有良好的析氧性能，超越了RuO2，在电解水方面有很好的应用前景。
本发明的制备方法原料简单易得、条件简便易行，所得的为纳米Ag修饰海胆状多孔碱式碳酸钴复合材料。
附图说明
图1为本发明上述复合材料(Ag/CCHH)的SEM图(a)和TEM照片(b)；
图2为本发明上述复合材料(Ag/CCHH)的LVS图。在扫速为5mV s-1，旋转速度为1600rpm时的各催化剂的极化曲线(实线：初始的LSVs；虚线为20CV循坏后的LSVs)。
具体实施方式
实施例1.纳米Ag修饰海胆状多孔碱式碳酸钴复合材料的制备
A.Ag胶体的制备。简单地说，45mg的AgNO3完全溶解在100mL的去离子水中，然后将溶液不断搅拌，在三颈圆底瓶中用回流冷凝器煮沸10分钟。随后，将1.0wt％柠檬酸钠溶液的4.5mL迅速注入上述系统，然后将混合物保持回流并强力搅拌15min，最后冷却到室温。
B.纳米Ag修饰海胆状多孔碱式碳酸钴(Ag∶CCHH摩尔比＝0.0261)复合材料制备。采用简单的溶剂热法，以预合成的Ag胶体为银源(模板剂)，研制Ag修饰的三维多孔海胆状CCHH的纳米复合材料。在一个典型的过程中，将Co(NO3)2·6H2O(0.145g，0.498mmol)和尿素(0.113g)溶解在乙醇(EA，20mL)和去离子水(20mL)的混合溶剂中，然后加入5mL预合成的Ag胶体(仅0.013mmol)。接下来，将所得混合物转移到50mL的聚四氟乙烯内衬不锈钢高压釜中，并在120℃下保持2小时。最后，冷却到室温后，通过离心、洗涤和干燥收集产品。制备的产物呈紫色灰色，标记为Ag/CCHH(0.013mmol)。
本实施例制得的Ag/CCHH(0.013mmol)复合材料，经XRD测定，峰的位置与强度与Ag和CCHH相匹配。因表明为Ag和CCHH复合物。
通过SEM照片(图1a)和TEM观察(图1b)，为由CCHH纳米棒构成的海胆结构，Ag纳米颗粒锚固在多孔CCHH纳米棒(直径约20-80nm、长度约为2-3微米)上。
Ag/CCHH(0.013mmol)复合材料LSV图，此时析氧性能超过RuO2，经20次循环伏安活化后，结果更优。结果见图2。
实施例2.纳米Ag修饰海胆状多孔碱式碳酸钴复合材料的制备
实验的步骤和试剂数量同实施例1，仅在溶剂热反应时间变为1h，可以得到类似结构的复合材料。
实施例3.纳米Ag修饰海胆状多孔碱式碳酸钴复合材料的制备
实验的步骤和试剂数量同实施例1，仅在溶剂热反应时间变为3h，可以得到类似结构的复合材料。
实施例4.纳米Ag修饰海胆状多孔碱式碳酸钴复合材料的制备
实验的步骤和试剂数量同实施例1，仅将Co(NO3)2·6H2O用0.498mmol的氯化亚钴(或醋酸亚钴)替代，溶剂热反应温度在120℃，时间为1-3小时，也可以制备获得类似纳米结构的复合材料。

Claims (3)

1.一种纳米Ag修饰海胆状多孔碱式碳酸钴复合材料，它为Ag颗粒锚固在多孔碱式碳酸钴纳米棒上，其中Ag颗粒尺寸20-25nm，纳米棒直径大约为25-80nm，长约2-3微米，这些纳米棒构成海胆状的微球，其直径约5微米。
2.一种制备权利要求1所述的复合材料的方法，其特征是：用事先制备的纳米Ag悬浊液，按一定的量加入到定量的Co(NO3)2·6H2O和尿素、水、乙醇混合溶液中，在120℃下，溶剂热反应1-3小时，经离心、洗涤、干燥获得产品。
3.一种制备权利要求1所述的复合材料的方法，其特征是：用事先制备的纳米Ag悬浊液，按一定的量加入到定量的氯化亚钴或醋酸亚钴和尿素、水、乙醇混合溶液中，在120℃下溶剂热反应1-3小时，经离心、洗涤、干燥获得产品。
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