Selective CO2 reduction to C3 and C4 oxyhydrocarbons on nickel phosphides at overpotentials as low as 10 mV†,Energy & Environmental Science

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Selective CO2 reduction to C3 and C4 oxyhydrocarbons on nickel phosphides at overpotentials as low as 10 mV†
Energy & Environmental Science ( IF 32.4 ) Pub Date : 2018-06-22 00:00:00 , DOI: 10.1039/c8ee00936h
Karin U. D. Calvinho _{1,

2,

3,

4} , Anders B. Laursen _{1,

2,

3,

4} , Kyra M. K. Yap _{1,

2,

3,

4} , Timothy A. Goetjen _{1,

2,

3,

4} , Shinjae Hwang _{1,

2,

3,

4} , Nagarajan Murali _{1,

2,

3,

4} , Bryan Mejia-Sosa _{2,

3,

4,

5} , Alexander Lubarski _{1,

2,

3,

4} , Krishani M. Teeluck _{1,

2,

3,

4} , Eugene S. Hall _{1,

2,

3,

4} , Eric Garfunkel _{1,

2,

3,

4} , Martha Greenblatt _{1,

2,

3,

4} , G. Charles Dismukes _{1,

2,

3,

4,

5}

Affiliation

We introduce five nickel phosphide compounds as electro-catalysts for the reduction of carbon dioxide in aqueous solution, that achieve unprecedented selectivity to C₃ and C₄ products (the first such report). Three products: formic acid (C₁), methylglyoxal (C₃), and 2,3-furandiol (C₄), are observed at potentials as low as +50 mV vs. RHE, and at the highest half-reaction energy efficiencies reported to date for any >C1 product (99%). The maximum selectivity for 2,3-furandiol is 71% (faradaic efficiency) at 0.00 V vs. RHE on Ni₂P, which is equivalent to an overpotential of 10 mV, with the balance forming methylglyoxal, the proposed reaction intermediate. P content in the series correlates closely with both the total C products and product selectivity, establishing definitive structure–function relationships. We propose a reaction mechanism for the formation of multi-carbon products, involving hydride transfer as the potential-determining step to oxygen-bound intermediates. This unlocks a new and more energy-efficient reduction route that has only been previously observed in nickel-based enzymes. This performance contrasts with simple metallic catalysts that have poor selectivity between multi-carbon products, and which require high overpotentials (>700 mV) to achieve comparable reaction rates.

中文翻译：

在低电位下将磷化镍上的 CO ₂选择性还原为C ₃和C _4的碳氢化合物†低至10 mV †

我们介绍了五种磷化镍化合物作为还原水溶液中二氧化碳的电催化剂，它们对C ₃和C ₄产物具有前所未有的选择性（第一个此类报告）。相对于RHE，在低至+50 mV的电势下以及在最高的半反应能效下，观察到三种产物：甲酸（C ₁），甲基乙二醛（C ₃）和2,3-呋喃二醇（C ₄）。迄今报告的任何> C1产品（99％）。与Ni _2上的RHE相比，在0.00 V下对2,3-呋喃二醇的最大选择性为71％（法拉第效率）P，相当于10 mV的超电势，其余部分形成甲基乙二醛（拟议的反应中间体）。系列中的P含量与总C产物和产物选择性密切相关，建立了确定的结构-功能关系。我们提出了形成多碳产物的反应机理，涉及氢化物转移作为确定氧结合中间体的电位的步骤。这开辟了一条新的且更具能源效率的还原途径，这种途径以前仅在镍基酶中才被观察到。该性能与简单的金属催化剂形成鲜明对比，该金属催化剂在多碳产物之间的选择性差，并且需要高的超电势（> 700 mV）才能达到可比的反应速率。

更新日期：2018-06-22

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