CN113416974A - 一种快速制备高效多孔银电催化剂的方法 - Google Patents
一种快速制备高效多孔银电催化剂的方法 Download PDFInfo
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Abstract
本发明涉及一种超均匀的纳米尺度高效多孔银电催化剂的制备方法。采用超高纯度的金属Ag和金属铜Cu作为原材料制备二元合金,设计合金原子比,采用金属熔融纺丝技术制备Ag15Cu85合金薄带。采用双级制备法,通过高温氧化对合金薄带进行表面改性处理,随后采用H2O2辅助的HCl溶液作为溶液脱合金介质制备超均匀纳米尺寸多孔银结构。高温氧化过程和H2O2辅助溶液的存在,极大地加快了合金薄带中活性组元的腐蚀进程,缩短了去合金时间,同时,高温氧化过程也为所制备的多孔结构提供了更多的催化活性位点,极大的提升了多孔银在电解水产氢过程中的催化效率。
Description
技术领域
本发明所涉及的是一种快速制备高效多孔银电催化剂的方法,是一种新型功能性纳米材料。该类材料界面特殊、比表面积高,在催化、传感、燃料电池等方面具有广泛应用,同时在储能、电催化等领域也展示出了不俗的潜力。氢气作为一种新型清洁能源,制备工艺简单,未来将成为替代化石能源的有力竞争者。
目前影响氢气主要通过电解水来制备,析氢电催化剂的加入能够极大的加速H原子的吸附和脱附过程,提高氢气制备效率,因此,一种快速制备高效多孔银电催化剂的方法将在氢能源的制备过程中大放异彩。
背景技术
纳米多孔金属材料是一类具有连通型纳米尺寸的三维双连续韧带/通道结构的材料。纳米级的三维双连续结构赋予了材料极高的比表面积和独特的物理、化学和力学等性能,因而在催化、传感等领域应用前景广阔。近年来,对于纳米多孔材料的研究大多停留在韧带/孔洞尺寸的优化、制备工艺的改良、腐蚀介质和前驱体合金的成分优化,以及脱合金机理的研究,而忽略了多孔结构在实际应用方面的研究。
目前,对于碳纳米支架、陶瓷纳米多孔泡沫、多孔金属氧化物和硫化物等的研究成果相对来说较多,而单金属纳米泡沫材料由于制备工艺复杂、时间成本高、合金成分要求严格,迄今在生产实践中后少有应用。此外,在纳米多孔金属材料方面,大部分研究重点在于纳米材料的制备工艺和去合金机理的研究,对于单金属纳米多孔结构在应用领域的研究还不够充分。
当下,商用的Pt/C电极是电解水制备氢气效率最高的电极催化剂。但是由于Pt的自然储量少,成本高,难以广泛应用,因此,替代Pt的低成本析氢电催化剂成为了催化领域的热点。纳米多孔材料比表面积高,在催化过程中能提供更多的催化活性位点,将会成为代替Pt催化剂的有力竞争者。
此外,现今已经出现的纳米材料的制备方法都是比较昂贵,时间成本较高,制备过程复杂,如电化学法、光还原法,溶胶凝胶法,化学电镀法,激光烧蚀法,粉末烧结,真空蒸镀法等。因此基于普通合金系统和简单工艺方法快速制备高效多孔银电催化剂的方法显得尤为重要。
发明内容
为了增强纳米多孔金属材料的电催化性能,缩短多孔结构的制备周期,本发明提出一种快速制备高效多孔银电催化剂的方法。
本发明的技术方案如下:
一种快速制备高效多孔银电催化剂的方法,其特征在于分别采用高温氧化和强氧化剂辅助酸性溶液制备超均匀、高催化活性的纳米多孔金属银。
一种快速制备高效多孔银电催化剂的方法包括以下步骤:
a) 采用惰性气体保护,通过金属熔融纺丝技术将99.99wt.%高纯铜、99.97wt.%纯银锭按设计的原子百分比制备成厚度约为50-100μm,宽度约为 1cm的二元合金薄带。
b) 采用高温箱式电阻炉对合金薄带进行表面改性处理,使合金薄带成分分布均匀,为制备超均匀多孔结构做准备;
c) 高温氧化改性过程的温度在500-800℃之间,选取合适的氧化持续时间;
d) 将高温氧化改性后的合金薄带置于强氧化剂辅助的酸性腐蚀液中,调整酸性腐蚀溶液的浓度、腐蚀时间,通过化学去合金法快速制备连通型三维双连续的高效多孔银电催化剂;
e) 将去合金后的纳米多孔材料从溶液中取出,用去离子水反复清洗试样至其PH值呈现中性,并用低温干燥箱烘干;
f)将所获得的超均匀纳米多孔银作为工作电极,置于酸性溶液中测试析氢电催化性能;
g) 检查双级去合金后的纳米多孔材料与前驱体宏观尺寸是否一致,对比单级制备的多孔银与双级分步法制备的多孔银的析氢催化性能。
a) 中的惰性气体为高纯氩气;
c)中氧化时间为5-120min;
d) 中强氧化性辅助溶液是浓度在1-30wt.% H2O2溶液、酸性腐蚀溶液的浓度为5-20 wt.% HCl、腐蚀时间为 0.1-10h、腐蚀温度为25-60℃。
本发明的优点效果如下:
本发明主要是采用双级去合金方法对预制合金进行选择性腐蚀制备出具有超均匀三维双连续的多孔结构的纳米银材料。简而言之:首先制备二元银-铜合金,设计合金成分原子比为Ag15Cu85;其次进行第一阶段高温氧化,设置合理的高温氧化时间和温度;最后进行第二阶段强氧化剂辅助酸溶液去合金,选择合适的腐蚀介质和去合金温度。由于初始状态的合金存在局部成分偏析,合金内部组织不均匀,这就意味着去合金之后形成的三维双连续的韧带/通道结构将会不均匀分布。本发明采用双级去合金方法,该方法的第一阶段实质就是通过高温氧化过程使初始合金薄带的成分均质化,此外,高温氧化过程中,活性组元发生氧化,这对加速脱合金过程起到了极大的促进作用。然后对第一阶段高温氧化去合金的产物进行强氧化剂辅助酸溶液去合金,氧化后的合金薄带表面的氧化产物在酸性条件下发生溶解在表面形成缺口,随后强氧化剂溶液从表面缺口进入合金内部氧化二元合金中的活性组元,氧化产物继续在酸性溶液中溶解,如此循环往复,而在此过程中,Ag原子扩散团聚形成了超均匀的三维双连续韧带/通道结构。由于高温氧化过程和去合金过程中强氧化剂的参与,所制备的纳米多孔银的表面活性位点更多,活性面积增大,极大的增强了纳米多孔银催化表现。
附图说明
图1为过氧化氢辅助盐酸去合金的工艺示意图。
图2为过氧化氢辅助盐酸去合金制备的超均质纳米多孔银形貌及其电解水析氢性能示意图。
具体实施方式
实施例 1
a) 采用惰性气体保护,通过金属熔融纺丝技术将99.99wt.%高纯铜、99.97wt.%纯银锭按设计的原子百分比制备成厚度约为50-100μm,宽度约为 1cm的二元合金薄带。
b) 采用高温箱式电阻炉对合金薄带进行表面改性处理,使合金薄带成分分布均匀,为制备超均匀多孔结构做准备;
c) 高温氧化改性过程的温度为650℃,选取合适的氧化持续1min;
d) 将高温氧化改性后的合金薄带置于强氧化剂辅助的酸性腐蚀液中,调整酸性腐蚀溶液的浓度、腐蚀时间,通过化学去合金法快速制备连通型三维双连续的高效多孔银电催化剂;
e) 将去合金后的纳米多孔材料从溶液中取出,用去离子水反复清洗试样至其PH值呈现中性,并用低温干燥箱烘干;
f)将所获得的超均匀纳米多孔银作为工作电极,置于酸性溶液中测试析氢电催化性能;
g) 检查双级去合金后的纳米多孔材料与前驱体宏观尺寸一致,双级分步法制备的多孔银的析氢Tafel斜率为45.8 mV dec-1。
a) 中的惰性气体为高纯氩气;
d) 中强氧化性辅助溶液是浓度在1-30wt.% H2O2溶液、酸性腐蚀溶液的浓度为5-20 wt.% HCl、腐蚀时间为 0.1-10h、腐蚀温度为25-60℃。
实施例 2
a) 采用惰性气体保护,通过金属熔融纺丝技术将99.99wt.%高纯铜、99.97wt.%纯银锭按设计的原子百分比制备成厚度约为50-100μm,宽度约为 1cm的二元合金薄带。
b) 采用高温箱式电阻炉对合金薄带进行表面改性处理,使合金薄带成分分布均匀,为制备超均匀多孔结构做准备;
c) 高温氧化改性过程的温度为650℃,选取合适的氧化持续1min;
d) 将高温氧化改性后的合金薄带置于强氧化剂辅助的酸性腐蚀液中,调整酸性腐蚀溶液的浓度、腐蚀时间,通过化学去合金法快速制备连通型三维双连续的高效多孔银电催化剂;
e) 将去合金后的纳米多孔材料从溶液中取出,用去离子水反复清洗试样至其PH值呈现中性,并用低温干燥箱烘干;
f)将所获得的超均匀纳米多孔银作为工作电极,置于酸性溶液中测试析氢电催化性能;
g) 检查双级去合金后的纳米多孔材料与前驱体宏观尺寸一致,双级分步法制备的多孔银的析氢Tafel斜率为46.67 mV dec-1。
a) 中的惰性气体为高纯氩气;
d) 中强氧化性辅助溶液是浓度在1-30wt.% H2O2溶液、酸性腐蚀溶液的浓度为5-20 wt.% HCl、腐蚀时间为 0.1-10h、腐蚀温度为25-60℃。
实施例 3
a) 采用惰性气体保护,通过金属熔融纺丝技术将99.99wt.%高纯铜、99.97wt.%纯银锭按设计的原子百分比制备成厚度约为50-100μm,宽度约为 1cm的二元合金薄带。
b) 采用高温箱式电阻炉对合金薄带进行表面改性处理,使合金薄带成分分布均匀,为制备超均匀多孔结构做准备;
c) 高温氧化改性过程的温度为650℃,选取合适的氧化持续1min;
d) 将高温氧化改性后的合金薄带置于强氧化剂辅助的酸性腐蚀液中,调整酸性腐蚀溶液的浓度、腐蚀时间,通过化学去合金法快速制备连通型三维双连续的高效多孔银电催化剂;
e) 将去合金后的纳米多孔材料从溶液中取出,用去离子水反复清洗试样至其PH值呈现中性,并用低温干燥箱烘干;
f)将所获得的超均匀纳米多孔银作为工作电极,置于酸性溶液中测试析氢电催化性能;
g) 检查双级去合金后的纳米多孔材料与前驱体宏观尺寸一致,双级分步法制备的多孔银的析氢Tafel斜率为47.72mV dec-1。
a) 中的惰性气体为高纯氩气;
d) 中强氧化性辅助溶液是浓度在1-30wt.% H2O2溶液、酸性腐蚀溶液的浓度为5-20 wt.% HCl、腐蚀时间为 0.1-10h、腐蚀温度为25-60℃。
Claims (6)
1.一种快速制备高效多孔银电催化剂的方法,其特征在于去合金之前采用高温氧化预处理进行表面改性,采用H2O2溶液辅助HCl溶液进行去合金过程。
2.制备权利要求1所述的一种快速制备高效多孔银电催化剂的方法,其特征在于包括以下步骤:
a) 采用惰性气体保护,通过金属熔融纺丝技术将99.99wt.%高纯铜、99.97wt.% 纯银锭按设计的原子百分比制备成厚度约为50-100μm,宽度约为 1cm的二元合金薄带。
3.b) 采用高温箱式电阻炉对合金薄带进行表面改性处理,使合金薄带成分分布均匀,为制备超均匀多孔结构做准备;
c) 高温氧化改性过程的温度在500-800℃之间,选取合适的氧化持续时间;
d) 将高温氧化改性后的合金薄带置于强氧化剂辅助的酸性腐蚀液中,调整酸性腐蚀溶液的浓度、腐蚀时间,通过化学去合金法快速制备连通型三维双连续的高效多孔银电催化剂;
e) 将去合金后的纳米多孔材料从溶液中取出,用去离子水反复清洗试样至其PH值呈现中性,并用低温干燥箱烘干;
f)将所获得的超均匀纳米多孔银作为工作电极,置于酸性溶液中测试析氢电催化性能;
g) 检查双级去合金后的纳米多孔材料与前驱体宏观尺寸是否一致,对比单级制备的多孔银与双级分步法制备的多孔银的析氢催化性能。
4.根据权利要求2所述的一种快速制备高效多孔银电催化剂的方法,其特征在于所述的步骤a)中的惰性气体为高纯氩气。
5.根据权利要求2所述的一种快速制备高效多孔银电催化剂的方法, 其特征在于所述的步骤c)中氧化时间为5-120min。
6.根据权利要求2所述的一种快速制备高效多孔银电催化剂的方法的制备方法,其特征在于所述的步骤d)中强氧化性辅助溶液是浓度在1-30wt.% H2O2溶液、酸性腐蚀溶液的浓度为5-20wt.% HCl、腐蚀时间为0.1-10h、腐蚀温度为25-60 ℃。
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