CN104593817B - 用于生产电化学合成气的表面改性电极 - Google Patents
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Abstract
本发明提供了一种用于生产电化学合成气的表面改性电极。具体地，提供了用于电化学还原二氧化碳和水而形成一氧化碳和氢的电极。所述电极包括金属基材。将自组装单层与金属基材结合。相对于裸金属基材来调节由电极产生的一氧化碳和氢的反应产物的选择性。
Description
技术领域
本发明涉及用于还原二氧化碳的电极，并且更特别地涉及用于还原二氧化碳的、具有在其上施加的自组装单层的电极。
背景技术
化石燃料是有限资源，其可以用于各种功能，例如燃料来源或各种产品的原料。化石燃料的燃烧增加环境中CO2的量。电解池可以用于在含水介质中电化学还原CO2以产生各种产物，例如H2、CO、醇类、甲酸、甲烷和短链烷烃。在这些产品中，H2和CO的混合物(合成气)是非常需要的，因为它可充当用于生产液态烃的商业费－托(Fischer-Tropsch)工艺的原料。在受控比例下选择性地生产H2和CO会有益于费－托工艺。
尽管已经开展了寻找用于还原CO2的高活性催化剂的许多研究，但是产物选择性控制仍然是需要解决的挑战。因此，在本领域中需要对于还原CO2可调节或控制H2和CO的产物选择性的电极。在本领域中还需要可调节或控制电极活性的电极。
发明内容
在一方面，公开了用于电化学还原二氧化碳和水而形成一氧化碳和氢的电极。所述电极包括金属基材。将自组装单层与金属基材结合。相对于裸金属基材来调节由电极产生的一氧化碳和氢的反应产物的选择性。
在另一方面，公开了用于电化学还原二氧化碳和水而形成一氧化碳和氢的电极。所述电极包括金属基材。将自组装单层与金属基材结合。所述自组装单层包括有机配体，所述有机配体具有表面端和相对端，所述表面端具有与金属基材结合的反应性基团，所述相对端包括有机官能团。相对于裸金属基材来调节由电极产生的一氧化碳和氢的反应产物的选择性。
在又一方面，公开了用于电化学还原二氧化碳和水而形成一氧化碳和氢的电极。所述电极包括金属基材。将自组装单层与金属基材结合。相对于裸金属基材来调节电极活性。
附图说明
图1是与金属基材连接的自组装单层的示意图；
图2是具有自组装单层的金金属基材的CV图表和包括各种有机官能团的配体的水接触角的测定，该自组装单层具有的配体与包括各种有机官能团的配体连接；
图3是具有自组装单层的银金属基材的CV图表，该自组装单层具有的配体与包括各种有机官能团的配体连接；
图4是具有自组装单层的银基材的恒电势极化的图表，该自组装单层具有的配体与包括各种有机官能团的配体连接；
图5是具有自组装单层的银基材的气相色谱图表和气相产物中氢和一氧化碳的百分比，该自组装单层具有的配体与包括各种有机官能团的配体连接；
图6是具有自组装单层的银和金基材的一氧化碳与氢的比例的图表，该自组装单层具有的C2和C11长度配体与包括各种有机官能团的配体连接；
图7是具有自组装单层的金基材的活性的图表，该自组装单层具有的C2和C11长度配体与包括各种有机官能团的配体连接；
图8是包括丝工作电极的实验电化学电池的示意图。
具体实施方式
参照图1，显示了用于电化学还原二氧化碳和水而形成一氧化碳和氢的电极10的示意图。该电极包括金属基材15。将自组装单层20与金属基材15结合。
在一方面，二氧化碳和水的电化学还原的反应产物可产生由一氧化碳和氢形成的合成气。该合成气可用于如通过下述反应详述的费－托工艺以生产各种烃材料。通过改变由电极产生的反应产物的选择性，可增加来自费－托工艺的所需烃的效率和产率。例如，对于液态烃燃料例如汽油的合成，可需要具有氢与一氧化碳2：1的比例。
(2n+1)H2+n CO→CnH(2n+2)+n H2O
所述金属基材15可由具有低的一氧化碳结合强度的金属形成。在一方面，可表征结合强度使得CO吸附能小于1eV。在一方面，所述金属可选自Au、Ag、Zn、Pd和Ga。
在一方面，所述自组装单层20包括有机配体25，该有机配体25具有表面端30和相对端40，表面端30具有与金属基材15结合的反应性基团35，相对端40包括有机官能团45。所述有机配体可具有C2至C20的碳单元长度。所述配体可由烷烃链或芳香族链形成。
在一方面，所述反应性基团与金属基材形成共价键。所述反应性基团可包括硫醇基团。所述反应性基团的硫醇基团可与所述金属基材的表面反应以形成共价键。如图1所示，将所述配体作为单层组装在金属基材上。
如上所述，所述相对端可包括可选自CH3、OH、COOH和NH2的有机官能团。在一方面，所述有机官能团可暴露于以二氧化碳饱和的含水电解质。所述各种有机官能团可影响电极的各种性质，包括疏水性以及电解质界面处的电荷。可以利用电极性质的变化来调节或改变所述电极的选择性和活性。
实施例
金(Au)和银(Ag)薄膜电极(厚度为100nm)由LGA薄膜公司(Santa Clara，CA)使用溅射法制备。为了提高附着力，在沉积Au或Ag膜之前，在玻璃基材上预溅射20-nm的Ti层。Ag丝电极(直径1.0mm)、硫醇基(thio－based)配体、碳酸氢钾(KHCO3)和乙醇购自SigmaAldrich。
电极的金属基材上的配体组装包括：清洁基材、制备配体溶液、用于组装的培育(incubation)和组装后的冲洗。为了清洁金属基材表面，首先在DI水中(5分钟，两次)然后在乙醇中(5分钟，两次)对所述电极进行声处理(sonicated)。对于Ag丝电极，在清洁工序之前，用50nm的Al2O3对该表面进行机械抛光。
在20ml玻璃瓶中将具有不同有机官能团的硫基配体以5mM的浓度溶解于乙醇中。如将在下文中更详细地讨论的，在以下实施例中利用C-2和C-11配体。在组装过程中，在室温下在配体溶液中浸渍和培育所有电极持续至少24小时。反应后，首先用乙醇冲洗电极，然后在乙醇和DI水中(每次冲洗5分钟，两次)对其进行声处理，随后在真空烘箱中在室温下进行干燥。将所得的电极储存在填充有氩的密封玻璃瓶中。
如图8所示，分别使用Pt网作为对电极和Ag/AgCl作为参比电极在两腔室槽中进行电化学分析。使用KHCO3(0.1M)作为电解质。在开始实验前，将CO2吹扫通过电解质至少15分钟。
参照图2和3，在Au和Ag金属基材的薄膜电极上进行循环伏安法研究和水接触角测量。Ag丝电极用于恒电势电解和GC分析。通过Nafion117片分隔阳极室和阴极室。在测试中，将25ml电解质填充到阳极室中，这允许顶部空间中的5.5ml气相体积。
基于如图2所详述的水接触角测量的结果，自组装单层(SAM)的形成是明显的。具有-COOH和-CH3基团的配体，分别给出最亲水和最疏水的表面。循环伏安法，如图2所示，相比于其它SAM-改性的表面和裸Au对照物，用SAM-COOH改性的电极产生更高的催化电流。
C-2和C-11配体还应用于Ag丝电极的改性，然后用于整体电解。为了检查作为对表面改性的反应的电极活性变化，在-0.8至-1.6V(相对于Ag/AgCl)的电势下进行恒电势电解。因为SAM配体具有非传导性的烷烃链，所以可以预期所述改性电极比空白对照物为更小活性的，如图4所示。这个结果证实了配体与Ag表面的连接。SAM改性电极比空白Ag对照物为更小活性的，这表明所述配体可能已产生用于电子转移的绝缘阻挡以影响电极的活性，使得可调节或控制该活性。
在总共通过1库伦电荷之后，通过气相色谱法(GC)测量在电化学电池顶部空间中H2和CO产物的量。如图5所示，SAM-改性对催化剂选择性具有显著的影响。对于具有不同的有机官能团的C-11配体，计算出的比例概括于图5的表中。令人感兴趣的是，从-COOH到–CH2OH和–CH3，H2与CO的比例增大，这与表面疏水性关联良好。此外，–NH2官能团显示出H2与CO的最高比例。这些结果证明，通过利用具有各种官能团的SAM改性电极来控制或调节产物选择性是可行的。
参照图6，显示了详细说明了对于具有施加至电极表面的SAM、并且包括各种官能团的银和金金属基材的一氧化碳与氢的比例的图表。该图表包括C-2和C-11长度配体两者。利用上述的实验装置，用CO2饱和的0.1M KHCO3作为电解质，在6.8的pH下，在-1.5V(相对于Ag/AgCl)的恒定电势下产生所述图表。从所述图表可以看出，可以选择配体长度、金属基材和有机官能团的选择来调节由电极产生的一氧化碳和氢的电极反应产物的选择性。
参照图7，显示了详细说明了对于具有施加至电极表面的SAM、并且包括各种官能团的金金属基材的活性的图表。该图表包括C-2和C-11长度配体。利用上述的实验装置，用CO2饱和的0.1M KHCO3作为电解质，在6.8的pH下，在-1.5V和-1.2V(相对于Ag/AgCl)的恒定电势下产生所述图表。从所述图表可以看出，可以选择配体长度、金属基材和有机官能团的选择来调节电极的活性。
已经以说明性方式描述了本发明。将理解的是，已使用的术语旨在处于描述的词语属性而不是限制。根据上述教导，本发明的许多修改和改变是可能的。因此，在所附权利要求的范围内，可以按具体描述以外的方式实施本发明。
Claims (5)
1.一种使用电极用于电化学还原二氧化碳和水而形成一氧化碳和氢的方法，包括：
提供由具有低的一氧化碳结合强度的金属形成的金属基材，该金属基材电化学还原二氧化碳和水；
提供与金属基材结合的自组装单层，其中该自组装单层包括有机配体，所述有机配体具有表面端和相对端，所述表面端具有与金属基材结合的反应性基团，所述相对端包括调节反应产物的比率的有机官能团；
其中所述有机功能团选自NH2和CH3，且氢与一氧化碳的比率大于3，或
其中所述有机官能团选自COOH，且氢与碳的比率为1，或
其中所述有机官能团选自OH，且氢与碳的比率大于1.5。
2.根据权利要求1所述的使用电极的方法，其中所述金属基材选自Au、Ag、Zn、Pd和Ga。
3.根据权利要求1所述的使用电极的方法，其中所述有机配体具有C2至C20的长度。
4.根据权利要求1所述的使用电极的方法，其中所述反应性基团与金属基材形成共价键。
5.根据权利要求1所述的使用电极的方法，其中所述反应性基团是硫醇基团。
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