BiZnx/Si光电阴极的制备及其CO2还原性能研究

doi:10.15541/jim20220027

无机材料学报 ›› 2022, Vol. 37 ›› Issue (10): 1093-1101.DOI: 10.15541/jim20220027 CSTR: 32189.14.10.15541/jim20220027

所属专题：【能源环境】CO2绿色转换(202312)

BiZn_x/Si光电阴极的制备及其CO₂还原性能研究

李成金¹^,²(), 薛怡¹^,², 周晓霞²(), 陈航榕²

1.上海理工大学材料与化学学院, 上海 200093
2.中国科学院上海硅酸盐研究所, 上海 200050

收稿日期:2022-01-17 修回日期:2022-04-18 出版日期:2022-10-20 网络出版日期:2022-04-26
通讯作者: 周晓霞, 副研究员. E-mail: zhouxiaoxia@mail.sic.ac.cn
作者简介:李成金 (1995-), 男, 硕士研究生. E-mail: ChengjinLL@163.com
基金资助:
国家自然科学基金(51961165107);上海国际合作项目(19520761000);上海市自然科学基金(19ZR1464500)

BiZn_x/Si Photocathode: Preparation and CO₂ Reduction Performance

LI Chengjin¹^,²(), XUE Yi¹^,², ZHOU Xiaoxia²(), CHEN Hangrong²

1. School of Materials and Chemistry, University of Shanghai for Science and Technology, Shanghai 200093, China
2. Shanghai Institute of Ceramics, Chinese Academy of Sciences, Shanghai 200050, China

Received:2022-01-17 Revised:2022-04-18 Published:2022-10-20 Online:2022-04-26
Contact: ZHOU Xiaoxia, associate professor. E-mail: zhouxiaoxia@mail.sic.ac.cn
About author:LI Chengjin (1995-), male, Master candidate. E-mail: ChengjinLL@163.com
Supported by:
National Natural Science Foundation of China(51961165107);Shanghai International Cooperation Project(19520761000);Shanghai Natural Science Foundation(19ZR1464500)

摘要/Abstract

摘要：

将CO₂转化为高附加值的化学品是实现碳循环, 缓解能源危机和环境问题的有效途径之一。金属与半导体复合电极, 利用光电耦合技术为CO₂转化提供了一种新思路。本研究通过电沉积的方法在碱刻蚀处理后的Si片上制备了双金属Bi、Zn共修饰的Si基光电阴极(BiZn_x/Si), 用于CO₂的光电催化还原。研究表明, 引入金属Bi和Zn能够改善光的吸收性能, 降低电化学阻抗, 提高电化学活性比表面积(ECSA)。其中, BiZn₂/Si最优的光电极电化学比表面积可达0.15 mF·cm^-2。除此之外, 研究发现双金属共同作用有助于增强电极对中间体*OCHO的吸附作用, 在-0.8 V(vs. RHE)电势下, 最优的光电阴极BiZn₂/Si生成HCOOH的法拉第效率高达96.1%。更重要的是, 光电阴极BiZn₂/Si的光电流强度在10 h内维持-13 mA·cm^-2, 表现出良好的性能稳定性。

关键词: CO₂还原, HCOOH, 光电极, BiZn_x

Abstract:

The conversion of CO₂ into high value-added chemicals is an effective way to realize the carbon cycle, alleviate energy crisis and environmental problems. The preparation of metal-semiconductor electrodes provides a new idea for CO₂ conversion by photoelectric coupling technology. In this study, Si was etched in alkali solution, on which a bimetallic Bi, Zn co-modified Si photoelectrocathode (BiZn_x/Si) was prepared via the electrodeposition process, for the photoelectrochemical reduction CO₂. The results show that the introduction of Bi and Zn can improve the light absorption performance, reduce the electrochemical impedance, and increase the electrochemical active surface area (ECSA). Especially, the ECSA of the best photoelectrocathode BiZn₂/Si is 0.15 mF·cm^-2. Besides, the cooperative effect of Bi and Zn can improve the adsorption performance toward the intermediates *OCHO. During the photoelectrochemical reduction of CO₂, the Faradaic efficiency for HCOOH reaches up to 96.1% on the best photoelectrocathode BiZn₂/Si at the potential of -0.8 V (vs. RHE). Moreover, the photocurrent intensity on the photoelectrocathode BiZn₂/Si remained -13 mA·cm^-2 during the 10 h photoelectric stability test, suggesting its high stability.

Key words: CO₂ reduction, HCOOH, photoelectrode, BiZn_x

中图分类号:

O611

李成金, 薛怡, 周晓霞, 陈航榕. BiZn_x/Si光电阴极的制备及其CO₂还原性能研究[J]. 无机材料学报, 2022, 37(10): 1093-1101.

LI Chengjin, XUE Yi, ZHOU Xiaoxia, CHEN Hangrong. BiZn_x/Si Photocathode: Preparation and CO₂ Reduction Performance[J]. Journal of Inorganic Materials, 2022, 37(10): 1093-1101.

图/表 24

图1 BiZnx/Si 光电阴极的制备及CO2还原过程示意图

Fig. 1 Schematic diagram of the fabrication of BiZnx/Si photoelectrocathode and CO2 reduction process

图2 光电化学CO2还原电解池的 (a) 实物照片和 (b) 模型示意图

Fig. 2 (a) Physical picture and (b) schematic model of photoelectrochemical cell for CO2 reduction

图3 (a) 未经处理的Si片、(b) 氢氧化钠碱溶液处理后的Si片、(c) Bi/Si、(d) BiZn1/Si、(e) BiZn2/Si和 (f) BiZn3/Si的SEM照片, (g~i) BiZn2/Si的元素分布图

Fig. 3 SEM images of (a) planar-Si, (b) Si treated with NaOH solution, (c) Bi/Si, (d) BiZn1/Si, (e) BiZn2/Si, and (f) BiZn3/Si with (g-i) elemental mappings of BiZn2/Si

图4 (a) Bi/Si、BiZn1/Si、BiZn2/Si和BiZn3/Si的 XRD图谱, (b) Planar-Si、Si-T、Bi/Si、BiZn1/Si、BiZn2/Si和BiZn3/Si的紫外-可见反射谱图

Fig. 4 (a) XRD patterns of Bi/Si, BiZn1/Si, BiZn2/Si, and BiZn3/Si, and (b) UV-Vis reflectivity spectra of Planar-Si, Si-T, Bi/Si, BiZn1/Si, BiZn2/Si and BiZn3/Si Colorful figures are available on website

图5 (a) Bi/Si、BiZn1/Si、BiZn2/Si和BiZn3/Si的Bi4f XPS精细谱图, (b) BiZn1/Si、BiZn2/Si和BiZn3/Si的Bi3+/Bi0比例, (c) BiZn2/Si的Zn2p XPS精细谱图

Fig. 5 (a) High resolution Bi4f XPS spectra of Bi/Si, BiZn1/Si, BiZn2/Si and BiZn3/Si, (b) ratios of Bi3+/Bi0 for BiZn1/Si, BiZn2/Si, and BiZn3/Si, and (c) high resolution Zn2p XPS spectrum for BiZn2/Si Colorful figures are available on website

图6 (a) Si-T、Bi/Si、BiZn1/Si、BiZn2/Si和BiZn3/Si的光电流响应曲线, (b)未经处理的Si片(Planar Si), Si-T、Bi/Si和BiZn2/Si在Ar和CO2饱和的0.5 mol·L-1 KHCO3溶液中的LSV曲线, Bi/Si、BiZn1/Si、BiZn2/Si和BiZn3/Si的 (c) 还原产物的法拉第效率柱状图和(d) HCOOH分电流密度, (e) Si-T、Bi/Si和BiZn2/Si的电化学阻抗谱图, (f) BiZn2/Si的10 h稳定性测试图

Fig. 6 (a) Transient photocurrent curves of Si-T, Bi/Si, BiZn1/Si, BiZn2/Si, and BiZn3/Si, (b) LSV curves of untreated Si (Planar Si), Si-T, Bi/Si, and BiZn2/Si in Ar or CO2-saturated 0.5 mol·L-1 KHCO3 aqueous solution, (c) FE histograms of CO2 reduction productions and (d) HCOOH current densities for Bi/Si, BiZn1/Si, BiZn2/Si, and BiZn3/Si, (e) electrochemical impedance spectra (EIS) of Si-T, Bi/Si and BiZn2/Si, and (f) stability of BiZn2/Si during 10 h test Colorful figures are available on website

图7 样品BiZn2/Si的PEC和EC CO2还原性能对比

Fig. 7 PEC and EC CO2 reduction performances of BiZn2/Si (a) Faradaic efficiency of CO2 reduction products; (b) HCOOH production rates; (c) EE. Colorful figures are available on website

图8 (a) Bi/Si、BiZn1/Si、BiZn2/Si和BiZn3/Si的ECSA数据, (b) 在0.1 mol·L-1 KOH溶液中, BiZn2/Si的PEC和EC CO2还原的氧化LSV曲线

Fig. 8 (a) ECSA lines of Bi/Si, BiZn1/Si, BiZn2/Si, and BiZn3/Si, and (b) oxidation LSV curves of PEC and EC CO2 reduction for BiZn2/Si in 0.1 mol·L-1 KOH aqueous solution

图9 CO2在光电阴极BiZn2/Si上形成HCOOH的机理示意图

Fig. 9 Mechanismic schematic of formation process of HCOOH on the photocathode BiZn2/Si Colorful figure is available on website

图S1 (a~d) Bi/Si和(e~h) BiZn2/Si的TEM 和HRTEM照片

Fig. S1 TEM and HRTEM images of (a-d) Bi/Si and (e-h) BiZn2/Si

图S2 BiZn2/Si的元素分布图

Fig. S2 Elemental distribution mapping of BiZn2/Si

图S3 (a) Bi/Si、(b) BiZn1/Si、(c) BiZn2/Si和(d) BiZn3/Si的电流-时间曲线

Fig. S3 i-t curves of (a) Bi/Si, (b) BiZn1/Si, (c) BiZn2/Si and (d) BiZn3/Si Colorful figures are available on website

图S4 (a~c) 气相色谱中H2、CO和O2的保留时间照片, (d) 液体产物的H1 NMR图谱

Fig. S4 (a-c) Images of retention time H2, CO and O2, (d) H1 NMR spectrum of liquid product

图S5 BiZn2/Si、Bi/Si和Zn/Si的CO2光电还原产物CO、H2和HCOOH的法拉第效率

Fig. S5 FE for PEC CO2 to CO, H2, HCOOH productions over BiZn2/Si, Bi/Si and Zn/Si

图S6 BiZn2/Si在CO2饱和的0.5 mol·L-1 KOH和Ar饱和的0.5 mol·L-1 KHCO3溶液中光电还原CO2反应后液相产物的1H NMR图谱

Fig. S6 1H NMR spectrum of the liquid phase products of BiZn2/Si in CO2-saturated 0.5 mol·L-1 KOH and Ar-saturated 0.5 mol·L-1 KHCO3 solutions for photoelechemical reduction of CO2

图S7 (a) BiZn2/Si、Bi/Si 和Si-T的光电流响应曲线, (b) BiZn2/Si、Bi/Si 和Si-T的荧光光谱图

Fig. S7 (a) Photocurrent curves of BiZn2/Si, Bi/Si and Si-T, (b) PL spectra of BiZn2/Si, Bi/Si and Si-T

图S8 BiZn2/Si在CO2饱和的0.5 mol·L-1 KHCO3溶液中的循环稳定性

Fig. S8 Cycling stability runs of BiZn2/Si in CO2-saturated 0.5 mol·L-1 KHCO3 solution

图S9 BiZn2/Si稳定性测试前后的 (a) XRD图谱和 (b) 稳定性测试后的SEM照片

Fig. S9 (a) XRD patterns of BiZn2/Si before and after stability test, (b) typical SEM image of BiZn2/Si after stability test

图S10 (a) Bi/Si、(b) BiZn1/Si、(c) BiZn2/Si和 (d) BiZn3/Si在不同扫描速率下的CV曲线

Fig. S10 CV curves for (a) Bi/Si, (b) BiZn1/Si, (c) BiZn2/Si and (d) BiZn3/Si at different scan rates

图S11 BiZn1/Si、BiZn2/Si和BiZn3/Si的LSV曲线

Fig. S11 LSV curves for BiZn1/Si, BiZn2/Si and BiZn3/Si

图S12 BiZn2/Si光电催化还原CO2反应前后的红外光谱图

Fig. S12 FT-IR spectra of BiZn2/Si before and after photoelectrochemical CO2 reduction reaction

图S13 BiZn2/Si、Bi/Si、Si-T的氧化LSV曲线

Fig. S13 Oxidation LSV curves of BiZn2/Si, Bi/Si and Si-T

表S1 ICP结果中不同样品的Bi/Zn摩尔比例

Table S1 Bi/Zn molar ratios of different samples in ICP results

Sample	BiZn₁/Si	BiZn₂/Si	BiZn₃/Si
(n)Bi/(n)Zn	142	120	88

表S2 不同光/电催化剂的法拉第效率和电流密度对比

Table S2 Faraday efficiency and current density comparison of different photo/electrocatalysts

Electrode	Electrolyte	E_app/V	J_total/(mA·cm^-2)	FE_formate	Ref.
Sn/SnO_x	0.5 mol·L^-1 KHCO₃	-0.7 vs. RHE	-2	~38% PEC	[1]
SnO₂	0.5 mol·L^-1 NaOH	-0.6 vs. RHE	-3.5	67.6% EC	[2]
Sn foil	0.5 mol·L^-1 KHCO₃	-2.0 vs. SCE	-28	63.5% EC	[3]
Sn dendrite	0.1 mol·L^-1 KHCO₃	-1.36 vs. RHE	-17.1	71.6% EC	[4]
Sn GDE	0.5 mol·L^-1 KHCO₃	-1. 8 vs. SCE	-22.2	78.6% EC	[5]
2,2’-bpy-coordinated Cu	0.5 mol·L^-1 KHCO₃	-1.2 vs. RHE	-15	57.7% PEC	[6]
Si/Bi5	0.5 mol·L^-1 KHCO₃	-1.03 vs. RHE	-24.1	72.1% PEC	[7]
Bi-PMo nanosheets	0.5 mol·L^-1 NaHCO₃	-0.86 vs. RHE	-30	93% EC	[8]
Bi₂O₃ nanoparticle	0.5 mol·L^-1 NaHCO₃	-1.2 vs. RHE	-22	91% EC	[9]
p-Si/Bi	0.5 mol·L^-1 NaHCO₃	-0.9 vs. RHE	-12	90% PEC	[10]
Bi nanoflakes	0.1 mol·L^-1 KHCO₃	-0.4 vs. RHE	-	79.5% EC	[11]
Cu₂₅In₇₅	0.5 mol·L^-1NaHCO₃	-0.7 vs. RHE	-	84.1% EC	[12]
In_1.5Cu_0.5 NPs	0.1 mol·L^-1 KHCO₃	-1.2 vs. RHE	-3.59	90% EC	[13]
This work	0.5 mol·L^-1 KHCO₃	-0.8 vs. RHE	-6.45	96.1% PEC	This work

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BiZn_x/Si光电阴极的制备及其CO₂还原性能研究

BiZn_x/Si Photocathode: Preparation and CO₂ Reduction Performance

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