Synergistic photoelectric and thermal effect for efficient nitrate reduction on plasmonic Cu photocathodes

doi:10.1016/S1872-2067(24)60060-4

Abstract

Abstract:

Recently, electrochemical nitrate reduction reaction (NO₃RR) has been intensively explored for the synthesis of ammonia, and copper (Cu) has become one of the most promising materials for NO₃RR. Notably, Cu is an important plasmonic metal that absorbs visible light. The plasmonic effect might have a significant influence on the performance of Cu-catalyzed NO₃RR but has been seldom reported. Herein, we report the synergistic photoelectric and thermal effect for efficient and stable NO₃RR on plasmonic Cu nanowire photocathodes, which is exclusively effective for NO₃RR but has no effect on the competing hydrogen evolution reaction. The faradaic efficiency for ammonia production is nearly 100% within a potential range from −0.2 V to −0.4 V vs. RHE, and a high ammonia yield rate of 1.37 mmol h⁻¹ cm⁻² is achieved at −0.2 V vs. RHE. Further operando photoelectrochemical studies and theoretical simulations confirm that the plasmonic excitation efficiently accelerates the rate-limiting desorption of NH₃ on Cu surfaces. We further demonstrate the versatility of this strategy to other Cu-based nanostructures.

Key words: Cu photocathodePlasmon-assisted electrocatalysis, Photoelectric effect, Photothermal effect, NO₃RR

Zhenlin Chen, Jing Xue, Lei Wu, Kun Dang, Hongwei Ji, Chuncheng Chen, Yuchao Zhang, Jincai Zhao. Synergistic photoelectric and thermal effect for efficient nitrate reduction on plasmonic Cu photocathodes[J]. Chinese Journal of Catalysis, 2024, 62: 219-230.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(24)60060-4

https://www.cjcatal.com/EN/Y2024/V62/I7/219

Figures/Tables 5

Fig. 1. (a) CV tests after 5 repetitive cycles under simulated solar irradiation (700 mW cm?2) in 0.5 mol L?1 Na2SO4 and 50 mmol L?1 NaNO3 at pH = 12 under 298 K. The CA tests of the Cu NWs at ?0.2 V vs. RHE with a stirring rate of 200 r min?1 under chopped irradiation with different light intensities (298 K) (b) and different temperatures (700 mW cm?2) (c). (d) A contour map of the current density under different light intensities and temperatures. (e) Apparent activation barriers of NO3RR in the dark (grey), under simulated solar irradiation (100 mW cm?2) (orange) and (700 mW cm?2) (red), and under 550 nm monochrome irradiation (700 mW cm?2) (blue). (f) The derivative current density versus time at the moment of turning on the light with different light intensities at 298 K.

Fig. 2. CV tests for the Cu NWs photocathode on repetitive cycling in 0.5 mol L?1 Na2SO4 and 50 mmol L?1 NaNO3 at pH = 12 at a scan rate of 50 mV s?1 in the dark (a) and under simulated solar irradiation (700 mW cm?2) (b). The cycle number is 5 both in the dark and under irradiation. (c) Intensity dependence of the peak current density at ?0.2 V vs. RHE of the 1st cycle and the 5th cycle extracted from the CV curves in 0.5 mol L?1 Na2SO4 and 50 mmol L?1 NaNO3. (d) Intensity dependence of the potential @1 mA cm?2 extracted from the CV curves in 0.5 mol L?1 Na2SO4 and 50 mmol L?1 NaNO3.

Fig. 3. (a) Yields of NH3 in the dark (blue) and under irradiation (red) at different potentials. (b) FE of NH3 (blue), H2 (purple), and NO2- (red) in the dark (dashed line), and under simulated solar irradiation (solid line) at different potentials. (c) FE of NH3 and NO2- and yields of NH3 in the dark and under irradiation in different concentrations of NO3-. (d) 1H NMR spectra before and after NO3RR using 15NO3- and 14NO3- electrolytes. (e) Recycle tests of the Cu NWs photocathode at ?0.2 V vs. RHE. (f) Calculated AQEs (red dots) under different monochromatic light irradiation and the UV-vis extinction spectrum (blue line) of the Cu NWs photocathode.

Fig. 4. (a) CA curves in 50 mmol L?1 NaNO3 in 0.5 mol L?1 PBS (blue) and 0.5 mol L?1 Na2SO4 (red) at ?0.2 V vs. RHE at pH = 10 under chopped irradiation. (b) The adsorption model and corresponding adsorption energy for NaNO3 and Na3PO4 on Cu surface. NO3RR intermediates were observed by DEMS analysis at ?0.2 V vs. RHE in 0.1 mol L?1 NaNO3 (c) and operando ATR-FTIR spectra under different potentials in 1 mol L?1 NaNO3 (d). (e) Free energy diagrams of NO3RR over Cu (111). (f) Charge density difference for the NH3 adsorbed on the Cu (111).

Fig. 5. CV tests for the Cu NP in 0.5 mol L?1 Na2SO4 and 50 mol L?1 NaNO3 at pH = 12, in the dark (a) and under simulated solar irradiation (700 mW cm?2) (b). (c) CA tests of the Cu NWs (red) and the Cu NP (blue) at ?0.2 V with under chopped simulated solar irradiation (700 mW cm?2). (d) FE of NH3 (red) and NO2? (blue) in the dark (dash line) and under irradiation (solid line) and yields for NH3 in the dark (blue) and under irradiation (red) for the Cu NP and the Cu NWs.

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