BiZnx/Si Photocathode: Preparation and CO2 Reduction Performance

doi:10.15541/jim20220027

Abstract

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

CLC Number:

O611

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.

Figures/Tables 24

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

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

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

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

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

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

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

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

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

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

Fig. S2 Elemental distribution mapping of BiZn2/Si

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

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

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

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

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

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

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

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

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

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

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

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

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 Photocathode: Preparation and CO₂ Reduction Performance

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