CN113564630A - 将金属气凝胶催化材料用于制备阴离子膜电解池电催化还原co2反应的用途 - Google Patents
将金属气凝胶催化材料用于制备阴离子膜电解池电催化还原co2反应的用途 Download PDFInfo
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Abstract
本发明属于化学催化技术领域,公开了将金属气凝胶催化材料用于制备阴离子膜电解池电催化还原CO2反应的用途。步骤包括:将新鲜配制的还原剂水溶液,快速加入金属前驱体溶液中,并持续搅拌一分钟,室温下静置反应得到水凝胶,随后冷冻干燥得到金属气凝胶;然后利用金属气凝胶制备阴极气体扩散电极,装配阴离子膜电解池,利用该阴离子膜电解池电催化二氧化碳还原反应,电解池使用阴离子膜将阴阳两极室隔开,阴极流场板为蛇形流场,阳极流场板为网状流场。利用金属气凝胶的阴极气体扩散电极,在阴离子膜电解池表现出优异的催化活性和稳定性,实现~80%的C1产物(HCOOH或CO)法拉第效率,电流密度>100mA cm‑2,具备工业化前景。
Description
技术领域
本发明属于电化学催化技术领域,具体涉及一种金属气凝胶催化材料的制备方法,并将金属气凝胶催化材料用于制备阴离子膜电解池电催化还原CO2反应的用途。
背景技术
随着二氧化碳(CO2)排放带来的环境问题日益加剧,以及碳中和概念的提出,针对CO2的治理已经提上了日程。从资源、能源发展战略的角度,以可再生电能或富余核电等洁净电能为能源,在温和的反应条件下,将CO2一步转化为碳氢化合物和醇类等高附加值燃料及化学品,同时实现CO2的高效转化和洁净电能的有效存储,将为可再生能源合理利用和CO2转化耦合提供极大的发展空间,为解决能源和环境资源的可持续发展做出极大的贡献。现有的商用电化学技术为CO2电催化转化(eCO2RR)提供了蓝图。
目前电催化CO2RR技术的工业化,除了政策外的影响因素,电解池的优化设计对于提高eCO2RR性能及其工业应用具有重要意义。电解池构型及其操作条件在很大程度上决定了电极附近的局部反应环境,从而调变催化性能。催化剂层作为电解池重要构件在电催化CO2RR过程中发挥着重要的作用。催化剂的组成直接关乎电催化CO2还原的产物选择性,其中CO引起了较大的关注,因为它是许多热化学、生物和电化学过程中常见的气体前体。CO和H2(合成气)的混合物可以作为目前实现费托合成或发酵过程的原料。当今最好的系统已经证明,CO的全电池能效约为40%至50%,接近具有成本竞争力的目标。与此同时CO作为气体产物,易于从电解质中析出,高法拉第效率的CO将有利于后期产物的分离和提纯,节约资金消耗,并且串联反应的搭建有望实现将直接放出的CO转化成商品化的产品。在CO之后,甲酸(HCOOH)是目前为止第二种动力学有利的CO2还原产物,并且HCOOH具有最高的经济价值,平均每摩尔电子的价值约为0.016$/mol e-,被广泛应用于农药、皮革、医药等工业。
借鉴燃料电池的阴离子交换膜的设计,构建的阴离子膜电解池可以大大降低阴极与阳极之间的电解液的欧姆损耗,提高器件工作效率,有工业化应用的潜能。但电解池运行过程中,催化剂通常会发生中毒、失活、水淹等现象。构建结构和化学性质稳定的催化剂对于电解池的高效、稳定运行非常关键。
发明内容
针对上述技术现状,本发明的目的在于提供一种应用于阴离子膜电解池中电催化还原CO2的金属气凝胶催化材料的制备方法,其技术路线简单、具有普适性并且拥有优异的电化学还原CO2的催化活性和选择性,也能推广作为其他电催化反应的催化剂。
本发明所提供的技术方案为:
将金属气凝胶催化材料用于制备阴离子膜电解池电催化还原CO2反应的用途,包括如下步骤:
(1)金属气凝胶催化材料的制备:
分别将金属前驱体和还原剂溶解在超纯水中,将新鲜配制的还原剂水溶液,快速加入金属前驱体溶液中,并持续搅拌一分钟,然后在室温下静置、老化得到水凝胶,随后在一定温度下冷冻干燥一段时间后得到用于阴离子膜电解池的金属气凝胶催化材料;
(2)阴极气体扩散电极的制备:
将步骤(1)制备的金属气凝胶或含金属气凝胶的复合材料加到含有Nafion溶液的醇类有机溶剂中形成均匀的催化剂墨水,将所得催化剂墨水通过浸渍或者喷涂的方式涂覆到疏水性碳纸上形成阴极气体扩散电极;
(3)阴离子膜电解池器件装配:
按照阴极流场板、阴极垫片、阴极气体扩散电极、阴离子膜、阳极材料、阳极垫片、阳极流场板的顺序进行装配,使得相邻部件之间保持良好的面接触;
(4)阴离子膜电解池器件测试:
将步骤(3)装配好的器件依次接好气液管路,电极接触线和控温装置,气体扩散电极浸渍在CO2饱和的水相电解液过夜,取出后使用超纯水洗涤以去除残留的电解液备用;
阴极流场直接通入干燥的CO2作为原料进入阴极的气体传输层,在气态CO2、液态电解液和固态催化剂的三相界面进行CO2还原反应。
步骤(1)中,所述金属前驱体为由银盐、金盐、钯盐、铋盐和锡盐中的任意一种或者几种金属盐组成;还原剂可以为硼氢化钠、硼氢化钾、抗坏血酸或者水合肼中的一种。
进一步地,
所述金属前驱体为由银的硝酸盐、硫酸盐、乙酸盐,金的氯化盐,钯的氯化盐、铋的硝酸盐和锡的氯化盐等任意一种或者几种金属盐组成。
所述还原剂的元电荷摩尔量与金属前驱体的元电荷摩尔量之比在1~2之间,金属前驱体溶液和还原剂水溶液的浓度均为0.05mol/L;冷冻干燥的温度为-50℃,时间为48h。
步骤(2)中,含金属气凝胶的复合材料指的是将金属气凝胶与碳材料进行复合,其中碳材料包括导电碳黑、碳纳米纤维、碳纳米管或石墨烯,所述醇类有机溶剂包括甲醇、乙醇、异丙醇。
步骤(3)中,所述阴离子膜为固体聚合物电解质(SPE)膜;所述阴极流场板采用蛇形流场,材质为石墨;阳极材料为商品铂电极;阳极流场板采用网状流场,材质为耐腐蚀金属钛。
步骤(4)中,所述的CO2饱和的水相电解液包括CO2饱和的NaHCO3溶液、KHCO3溶液、KCl溶液、K2SO4溶液、磷酸盐缓冲溶液或者硼酸盐缓冲溶液。
本发明的设计思想为:
本发明通过溶胶-凝胶方法得到金属气凝胶,金属离子首先被还原剂快速还原为金属纳米颗粒,金属纳米颗粒会因要降低体系的表面能进行奥斯特瓦尔德熟化过程来自发组装凝胶,在自组装之后气凝胶的纳米网络中会出现晶界以及缺陷,有利于催化活性的提升,结合阴离子膜电解池以此来实现工业相关电流密度。
实验证实,本发明提供的用于阴离子膜电解池的金属气凝胶催化材料的制备方法具有以下特点和优点:
(1)制备得到的金属气凝胶具有优良的电催化还原CO2反应的催化活性。
(2)与已经报道的催化材料相比,稳定的金属气凝胶的三维结构避免了催化剂的团聚和因腐蚀中毒而失活。
(3)金属气凝胶本征的疏松多孔特性可以有效防止电解质/溶质堵塞孔道导致的传质受阻。
(4)本发明提供的制备方法具有普适性,可以制备多种单/双金属气凝胶,例如:Au气凝胶催化剂、Ag气凝胶催化剂、Pd气凝胶催化剂、Bi/Sn气凝胶催化剂及Ag/Pd气凝胶催化剂等。
(5)利用本发明的方法制备的金属气凝胶及含金属气凝胶复合材料用作阴极催化剂应用于电催化CO2还原反应中,搭配阴离子膜电解池可以获得高的电催化活性和稳定性,在实现工业相关电流密度(>100mA cm-2)的同时减少了欧姆损耗,电催化CO2RR的C1产物(HCOOH或CO)法拉第效率能在大电势窗口下维持在80%。
附图说明
图1为实施例1所制备的金属气凝胶的XRD图。
图2为实施例1所制备的金属气凝胶的SEM图。
图3为实施例1所制备的金属气凝胶的TEM图。
图4为实施例1,2,3所制备的金属气凝胶电化学还原CO2为CO的法拉第效率图。
图5为实施例1所制备的阴极气体扩散电极的接触角图。
具体实施方式:
实施例1:
首先,称取硝酸银和还原剂分别溶于超纯水中,配制成浓度为0.05mol/L的溶液,其中还原剂为硼氢化钠。取10mL的硝酸银溶液置于30mL的反应瓶中,随后在450rpm的搅拌速度下快速加入15mL的硼氢化钠溶液,一分钟后停止搅拌,置于室温下8h进行自发凝胶。凝胶结束使用去离子水小心洗涤五次,后将水凝胶使用液氮冷冻,随后置于冷冻干燥机中-50℃干燥48h后得到银气凝胶。
称取5mg银气凝胶和1mg的导电碳黑溶于950μL异丙醇和50μL的5wt%Nafion溶液中,超声1h得到混合均匀的催化剂墨水,取100μL的催化剂墨水涂覆在疏水碳纸上作为阴离子膜电解池的阴极气体扩散电极用于电催化CO2还原。将气体扩散电极浸渍在CO2饱和的KHCO3水溶液中过夜,然后用超纯水洗涤除去电解液杂质。按照有机玻璃板-不锈钢板-阴极石墨流场-硅橡胶垫片-阴极气体扩散电极-阴离子膜-铂电极-硅橡胶垫片-阳极钛流场-有机玻璃板的顺序进行电解池装配,各零部件之间使用螺丝拧紧,阳极加入纯水。安装好接线和管路,在常温条件下阴极持续通入100sccm的CO2干气,随后通电测试。测试结果表明,负载在气体扩散电极上的银气凝胶复合材料能在-0.79~-1.09V(vs.RHE)的大电势窗口下保持~80%的CO法拉第效率,并且能产生高达100mA/cm2的电流密度且稳定性良好,可以满足工业需求。
实施例2:
首先称取硝酸银和还原剂溶质分别溶于超纯水中,配制成浓度为0.05mol/L的溶液,其中还原剂为硼氢化钾。取10mL的硝酸银溶液置于30mL的反应瓶中,随后在450rpm的搅拌速度下快速加入10mL的硼氢化钾溶液,一分钟后停止搅拌,置于室温下8h进行自发凝胶。凝胶结束使用去离子水小心洗涤五次后将水凝胶使用液氮冷冻,随后置于冷冻干燥机中-50℃干燥48h后得到银气凝胶。
其性能指标如下:称取5mg银气凝胶和1mg的碳纳米管溶于950μL乙醇和50μL的5wt%Nafion溶液中,超声1h得到混合均匀的催化剂墨水,取100μL的催化剂墨水涂覆在疏水碳纸上作为阴离子膜电解池的阴极气体扩散电极用于电催化CO2还原。将气体扩散电极浸渍在CO2饱和的K2SO4水溶液中过夜,然后用超纯水洗涤除去电解液杂质。按照有机玻璃板-不锈钢板-阴极石墨流场-硅橡胶垫片-阴极气体扩散电极-阴离子膜-铂电极-硅橡胶垫片-阳极钛流场-有机玻璃板的顺序进行电解池装配,各零部件之间使用螺丝拧紧,阳极加入纯水。安装好接线和管路,在常温条件下阴极持续通入100sccm的CO2干气,随后通电测试。测试结果表明,负载在气体扩散电极上的银气凝胶复合材料能在-0.79~-0.99V(vs.RHE)的电势窗口下保持~73%的CO法拉第效率,有着优良的电化学还原CO2至CO的催化选择性。
实施例3:
首先称取硝酸银和还原剂溶质分别溶于超纯水中,配制成浓度为0.05mol/L的硝酸银水溶液和还原剂溶液,其中还原剂为水合肼。取10mL的硝酸银溶液置于30mL的反应瓶中,随后在450rpm的搅拌速度下快速加入20mL的水合肼溶液,一分钟后停止搅拌,置于室温下8h进行自发凝胶。凝胶结束使用去离子水小心洗涤五次后将水凝胶使用液氮冷冻,随后置于冷冻干燥机中-50℃干燥48h后得到银气凝胶。
其性能指标如下:称取5mg银气凝胶溶于950μL乙醇和50μL的5wt%Nafion溶液中,超声1h得到混合均匀的催化剂墨水,取100μL的催化剂墨水涂覆在疏水碳纸上作为阴离子膜电解池的阴极气体扩散电极用于电催化CO2还原。将气体扩散电极浸渍在CO2饱和的KH2PO4水溶液中过夜,然后用超纯水洗涤除去电解液杂质。按照有机玻璃板-不锈钢板-阴极石墨流场-硅橡胶垫片-阴极气体扩散电极-阴离子膜-铂电极-硅橡胶垫片-阳极钛流场-有机玻璃板的顺序进行电解池装配,各零部件之间使用螺丝拧紧,阳极加入纯水。安装好接线和管路,在常温条件下阴极持续通入100sccm的CO2干气,随后通电测试。测试结果表明,负载在气体扩散电极上的银气凝胶能在-0.89~-0.99V(vs.RHE)的电势窗口下保持~65%的CO法拉第效率。
以上所述的实施例对本发明的技术方案进行了详细说明,应理解的是以上实例所述仅为本发明的技术方案而非对本发明的保护范围的限制,尽管参照较佳实施例对本发明做了详细说明,凡在本发明的原则范围内所作的任何修改、补充或类似方式替代等,均应包含在本发明的保护范围之内。
图1是银气凝胶的XRD图,图中2θ值为38.20°,44.40°,64.60°,77.60°处的尖峰,分别为Ag(111)、Ag(200)、Ag(220)和Ag(311)的晶面(JCPDS 87-0718)。
从图2的SEM图可知,银气凝胶展现出了多孔结构,能在催化反应中暴露更多的活性位点、促进传质并提高了催化剂的稳定性。
图3是银气凝胶的TEM图,从图中可以看出银气凝胶是由银纳米颗粒自发组装而成的,且在凝胶过程中因取向不同造成了大量作为催化位点的晶界的存在。
图4为银气凝胶作为电化学还原CO2的催化剂时的CO法拉第效率,实例1在-0.79~-1.09V(vs.RHE)的大电势窗口下对CO的法拉第效率高达80%,显示出了优异的电化学还原CO2的催化活性。实例2在-0.79~-0.99V(vs.RHE)的电势窗口下保持~73%的CO法拉第效率,实例3在-0.89~-0.99V(vs.RHE)的电势窗口下保持~65%的CO法拉第效率。
图5为阴离子膜电解池气体扩散电极的接触角图,从图中可以看出工作电极与水的接触角为125.0°,电极表面展现出疏水性质,在电催化CO2还原中可以有效地减少与水的接触并抑制析氢竞争反应的发生。
Claims (7)
1.将金属气凝胶催化材料用于制备阴离子膜电解池电催化还原CO2反应的用途,其特在于,包括如下步骤:
(1)金属气凝胶催化材料的制备:
分别将金属前驱体和还原剂溶解在超纯水中,将新鲜配制的还原剂水溶液,快速加入金属前驱体溶液中,并持续搅拌,然后在室温下静置、老化得到水凝胶,随后在一定温度下冷冻干燥一段时间后得到用于阴离子膜电解池的金属气凝胶催化材料;
(2)阴极气体扩散电极的制备:
将步骤(1)制备的金属气凝胶或含金属气凝胶的复合材料加到含有Nafion溶液的醇类有机溶剂中形成均匀的催化剂墨水,将所得催化剂墨水通过浸渍或者喷涂的方式涂覆到疏水性碳纸上形成阴极气体扩散电极;
(3)阴离子膜电解池器件装配:
按照阴极流场板、阴极垫片、阴极气体扩散电极、阴离子膜、阳极材料、阳极垫片、阳极流场板的顺序进行装配,使得相邻部件之间保持良好的面接触;
(4)阴离子膜电解池器件测试:
将步骤(3)装配好的器件依次接好气液管路,电极接触线和控温装置,气体扩散电极浸渍在CO2饱和的水相电解液过夜,取出后使用超纯水洗涤以去除残留的电解液备用;
阴极流场直接通入干燥的CO2作为原料进入阴极的气体传输层,在气态CO2、液态电解液和固态催化剂的三相界面进行CO2还原反应。
2.如权利要求1所述的用途,其特征在于,步骤(1)中,所述金属前驱体为由银盐、金盐、钯盐、铋盐和锡盐中的任意一种或者几种金属盐组成;还原剂可以为硼氢化钠、硼氢化钾、抗坏血酸或者水合肼中的一种。
3.如权利要求2所述的用途,其特征在于,所述金属前驱体为由银的硝酸盐、硫酸盐、乙酸盐,金的氯化盐,钯的氯化盐、铋的硝酸盐和锡的氯化盐等任意一种或者几种金属盐组成。
4.如权利要求1所述的用途,其特征在于,步骤(1)中,所述还原剂的元电荷摩尔量与金属前驱体的元电荷摩尔量之比在1~2之间,金属前驱体溶液和还原剂水溶液的浓度均为0.05mol/L;持续搅拌的时间为一分钟,冷冻干燥的温度为-50℃,时间为48h。
5.如权利要求1所述的用途,其特征在于,步骤(2)中,含金属气凝胶的复合材料指的是将金属气凝胶与碳材料进行复合,其中碳材料包括导电碳黑、碳纳米纤维、碳纳米管或石墨烯,所述醇类有机溶剂包括甲醇、乙醇、异丙醇。
6.如权利要求1所述的用途,其特征在于,步骤(3)中,所述阴离子膜为固体聚合物电解质(SPE)膜;所述阴极流场板采用蛇形流场,材质为石墨;阳极材料为商品铂电极;阳极流场板采用网状流场,材质为耐腐蚀金属钛。
7.如权利要求1所述的用途,其特征在于,步骤(4)中,所述的CO2饱和的水相电解液包括CO2饱和的NaHCO3溶液、KHCO3溶液、KCl溶液、K2SO4溶液、磷酸盐缓冲溶液或者硼酸盐缓冲溶液。
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