Effect of pressure and temperature on carbon dioxide reduction at a plasmonically active silver cathode
Effect of pressure and temperature on carbon dioxide reduction at a plasmonically active silver cathode
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压力和温度对等离子体活性银阴极二氧化碳还原的影响
DOI：
10.1016/j.electacta.2021.137820
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发表时间：
2021
影响因子：
6.6
通讯作者：
McCloskey, Bryan D.
中科院分区：
文献类型：
--
作者：
Corson, Elizabeth R.;Creel, Erin B.;Kostecki, Robert;Urban, Jeffrey J.;McCloskey, Bryan D.
通过在黑暗和光照条件下改变压力和温度，研究了等离子体增强的银阴极上CO2还原的选择性变化机理.在线性扫描伏安法和计时电流法中，在− 0.7、− 0.9和− 1.1 V RHE下研究了0.2至1 atm范围内的CO2分压（P CO2）。在一定的外加过电位下，无论在黑暗还是在光照条件下，总电流密度均随PCO 2的增加而增加，但Tafel行为在黑暗和光照条件下存在显著差异。在黑暗和光照条件下，CO2还原为一氧化碳（CO）的反应在所有外加电位下均表现为一级动力学行为，这可能表明光照条件下的速率决定步骤没有变化。在黑暗中，并在每个应用的电位的光下，氢（H 2）的析出反应的活性随着P CO 2的增加而降低，这使得它不清楚，如果光是影响CO或H 2中间吸附物的覆盖率略有不同。在任何条件下，甲酸和甲醇的生成都不依赖于PCO 2，但真正的反应级数可能被银阴极上CO和H2的高活性所掩盖。在-0.7 V、-0.9 V和-1.1 V RHE条件下，在黑暗和光照条件下，对14、22和32 ℃温度下产物分布的研究表明，在光照条件下观察到的选择性变化不是由阴极表面的局部加热引起的。
Carbon dioxide (CO 2) reduction at a plasmonically active silver cathode was investigated by varying the pressure and temperature at multiple applied potentials under both dark and illuminated conditions to understand the mechanism of selectivity changes driven by plasmon-enhanced electrochemical conversion. CO 2 partial pressures (P CO 2) from 0.2 to 1 atm were studied during linear sweep voltammetry and chronoamperometry at− 0.7,− 0.9, and− 1.1 V RHE. At a given applied overpotential the total current density increased with increasing P CO 2 in both the dark and the light, but there were significant differences in the Tafel behavior between dark and illuminated conditions. The reduction of CO 2 to carbon monoxide (CO) was found to have first-order behavior with respect to P CO 2 at all applied potentials in both the dark and the light, likely indicating no change in the rate-determining step upon illumination. Activity for the hydrogen (H 2) evolution reaction decreased with increasing P CO 2 at slightly different rates in the dark and the light at each applied potential, making it unclear if light is influencing CO or H 2 intermediate adsorbate coverage. Both formate and methanol production showed no dependence on P CO 2 under any conditions, but the true reaction orders may be masked by the much higher activity for CO and H 2 at the silver cathode. The investigation of product distribution with temperature at 14, 22, and 32∘ C at− 0.7,− 0.9, and− 1.1 V RHE in both the dark and the light demonstrated that the selectivity changes observed upon illumination are not caused by local heating of the cathode surface.
影响因子：
8.4
作者：
S. Rybchenko;D. Touhami;J. Wadhawan;S. Haywood
通讯作者：
S. Rybchenko;D. Touhami;J. Wadhawan;S. Haywood
含氧二氧化碳原料电化学还原过程中传质的保护作用
影响因子：
5.6
作者：
Kindle Williams;Nathan Corbin;Joy S. Zeng;Nikifar Lazouski;Dengtao Yang;Karthish Manthiram
通讯作者：
Karthish Manthiram
影响因子：
22
作者：
Creel, Erin B.;Corson, Elizabeth R.;McCloskey, Bryan D.
通讯作者：
McCloskey, Bryan D.