氮掺杂碳限域的花状SnS催化CO2电还原制甲酸

doi:10.16085/j.issn.1000-6613.2022-0037

摘要/Abstract

摘要：

合理设计高效的电催化剂是二氧化碳电化学还原（CO₂ER）为高附加值化学品和燃料的关键。本文利用水热-煅烧法制备了氮掺杂碳限域的花状SnS催化剂（SnS@NC）并研究了其电催化CO₂的特性。基于超薄氮掺杂碳层的限域效应，SnS的层厚由原始的30nm缩减至20nm，电化学活性面积明显增强，同时氮掺杂碳层增强了对CO₂的吸附和活化。SnS@NC催化CO₂转化为甲酸的能力明显增强，在-1.3V（vs. RHE）的H型电解池中法拉第效率为81.2%，电流密度为29.5mA/cm²，本文为金属硫化物复合催化剂功能化提供了新策略。

关键词: 电化学, 还原, 二氧化碳, 硫化锡, 氮掺杂碳

Abstract:

Rational design of efficient electrocatalysts is critical for electrochemical reduction of carbon dioxide (CO₂ER) to high value-added chemicals and fuels. Herein, a hydrothermal-calcination method was developed to prepare flower-like SnS catalyst confined by nitrogen-doped carbon (SnS@NC) and the CO₂ER performance of SnS@NC was studied. Based on the confinement effect of the ultra-thin nitrogen-doped carbon layer, the layer thickness of SnS nanosheet was reduced from the original 30nm to 20nm, and the electrochemically active area was significantly increased. At the same time, the nitrogen-doped carbon layer could enhance the adsorption and activation of CO₂. As a result, the CO₂-to-HCOOH conversion over SnS@NC was significantly enhanced. The SnS@NC provided an HCOOH Faraday efficiency of 81.2% at -1.3V(vs. RHE), and a current density up to 29.5mA/cm² in the H-type electrolytic cell. This work could provide a novel strategy for the functionalization of metal-sulfide based catalysts.

Key words: electrochemistry, reduction, carbon dioxide, tin disulfide, nitrogen-doped carbon

中图分类号:

O643.3

黄鑫, 刘成, 唐如佳, 韩欣欣, 陈世霞, 王珺. 氮掺杂碳限域的花状SnS催化CO₂电还原制甲酸[J]. 化工进展, 2022, 41(11): 5887-5895.

HUANG Xin, LIU Cheng, TANG Rujia, HAN Xinxin, CHEN Shixia, WANG Jun. Nitrogen-doped carbon-confined flower-like SnS catalyst for electrochemical reduction of CO₂ to HCOOH[J]. Chemical Industry and Engineering Progress, 2022, 41(11): 5887-5895.

图/表 7

图1 SnS@NC的合成示意图

图2 SnS、SnS@C的SEM图以及SnS@NC的SEM图、TEM图和EDX扫描图

图3 样品的XRD图和拉曼光谱图以及XPS高分辨能谱图

表1 XPS所测得的材料表层Sn、S、N、C各原子的占比

样品	N/%	C/%	Sn/%	S/%
SnS	2.09	64.22	18.11	15.15
SnS@C	2.29	82.40	7.23	8.08
SnS@NC	2.66	83.64	6.38	7.33

图4 扫描速率为10mV/s时，催化剂在N2（虚线）和CO2（实线）饱和0.5mol/L KHCO3电解液的LSV曲线和不同电位下各电极在CO、HCOOH和H2中的法拉第效率和电流密度以及本文所开发的材料与文献中报道的锡基催化剂性能比较图

图5 各样品的双电层电容的确定和塔菲尔图以及SnS和SnS@NC的电解质接触角

图6 SnS@NC稳定性测试的结果

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氮掺杂碳限域的花状SnS催化CO₂电还原制甲酸

Nitrogen-doped carbon-confined flower-like SnS catalyst for electrochemical reduction of CO₂ to HCOOH

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