协同光电及热效应实现铜光阴极上等离激元催化高效硝酸根还原反应

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

催化学报 ›› 2024, Vol. 62: 219-230.DOI: 10.1016/S1872-2067(24)60060-4

协同光电及热效应实现铜光阴极上等离激元催化高效硝酸根还原反应

陈振霖^a^,^b^,¹, 薛静^a^,^b^,¹, 武磊^a^,^b, 党昆^a^,^b, 籍宏伟^a^,^b, 陈春城^a^,^b, 章宇超^a^,^b^,^*(), 赵进才^a^,^b

^a中国科学院化学研究所光化学重点实验室, 北京分子科学国家研究中心, 北京 100190
^b中国科学院大学, 北京 100049

收稿日期:2024-03-22 接受日期:2024-05-27 出版日期:2024-07-18 发布日期:2024-07-10
通讯作者: *电子信箱: yczhang@iccas.ac.cn (章宇超).
作者简介:¹共同第一作者.
基金资助:
国家重点研发计划(2022YFA1505000);国家重点研发计划(2020YFC1808401);国家自然科学基金(22072158);国家自然科学基金(22321004);中国科学院战略重点研究项目(XDB36000000);中国科学院基础研究青年科学家项目(YSBR-004)

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

Zhenlin Chen^a^,^b^,¹, Jing Xue^a^,^b^,¹, Lei Wu^a^,^b, Kun Dang^a^,^b, Hongwei Ji^a^,^b, Chuncheng Chen^a^,^b, Yuchao Zhang^a^,^b^,^*(), Jincai Zhao^a^,^b

^aKey Laboratory of Photochemistry, Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
^bUniversity of Chinese Academy of Sciences, Beijing 100049, China

Received:2024-03-22 Accepted:2024-05-27 Online:2024-07-18 Published:2024-07-10
Contact: *E-mail: yczhang@iccas.ac.cn (Y. Zhang).
About author:¹ Contributed equally to this work.
Supported by:
National Key R&D Program of China(2022YFA1505000);National Key R&D Program of China(2020YFC1808401);National Natural Science Foundation of China(22072158);National Natural Science Foundation of China(22321004);Strategic Priority Research Program of the Chinese Academy of Sciences(XDB36000000);CAS Project for Young Scientists in Basic Research(YSBR-004)

摘要/Abstract

摘要：

近年来, 电催化硝酸根还原反应(NO₃RR)已经成为水处理和合成氨领域的研究热点. 相比于传统的电催化剂, 等离激元辅助的电催化反应通过将太阳能和电化学偏压同时施加到金属纳米结构上, 在实现高效太阳能到化学能转化领域展现出了巨大潜力. 然而, 目前有关等离激元辅助NO₃RR的文献报道较少, 已有的研究主要集中于利用金(Au)纳米结构的等离激元效应辅助增强NO₃RR. 但Au对NO₃RR的本征电催化活性很差, 这导致在等离激元辅助NO₃RR领域, 氨的产率和法拉第效率难以令人满意. 此外, 对于等离激元辅助NO₃RR的机理研究不深入, 例如如何区分等离激元产生的光电效应和光热效应对NO₃RR的影响, 以及等离激元激发的金属纳米结构是如何影响NO₃RR过程等问题都尚未解决. 因此, 有必要采取有效的策略来深入探究等离激元辅助NO₃RR的内在机制, 从而进一步提高其催化性能.

铜(Cu)作为一种高效的硝酸根还原电催化剂, 同时是一种典型的具有等离激元效应的金属材料. 然而, 目前关于利用Cu的等离激元效应辅助增强NO₃RR的报道很少. 本文报道了利用Cu纳米线(Cu NWs)的等离激元效应辅助增强NO₃RR性能. 在等离激元激发条件下, Cu NWs展现出较好的NO₃RR催化性能. 在协同的光电和热效应的作用下, 与暗态常温条件相比, 催化性能提升了近2倍. 经过400次循环伏安测试, Cu NWs光阴极的电流密度仅下降到初始值的88%, 而在黑暗条件下, Cu NWs光阴极催化NO₃RR的电流密度则下降了43%. 这表明光照同时显著提升了Cu NWs催化NO₃RR的稳定性. 产物分析结果表明, 在−0.2到−0.4 V (相对于可逆氢电极)的宽电势范围内, Cu NWs光阴极实现了接近100%的氨法拉第效率, 并取得了较高的氨产率, 超过了之前大多数报道的等离激元辅助Au催化剂的NO₃RR性能. 通过活化能实验、微分电流实验以及升温实验, 区分了等离激元激发产生的光电效应以及光热效应对NO₃RR的影响. 通过原位拉曼光谱、在线差分电化学质谱以及原位电化学红外光谱技术, 确定了Cu NWs光阴极NO₃RR过程中的活性相及反应中间体. 密度泛函理论计算结果表明, 氨的脱附是NO₃RR的决速步. 光生电子可以通过电子跃迁激发脱附机制促进氨的脱附从而抑制了氨在Cu表面的累积, 弱化了氨对Cu NWs光阴极的毒化作用. 同时, 光热效应也显著提升了NO₃RR的反应速率. 因此, 等离激元激发产生的光电和光热效应协同促进了NO₃RR性能, 提高了Cu NWs光阴极的活性与稳定性. 将该策略拓展到其它Cu纳米材料上, 同样展现出较好的等离激元促进效果.

综上, 本文提出了利用Cu的等离激元效应辅助增强电催化NO₃RR性能的策略, 并验证了该策略在其它Cu纳米材料上的适用性. 深入的机理研究揭示了同时耦合太阳能、电能以及热能对进一步提升NO₃RR性能的巨大潜力.

关键词: 铜光阴极, 等离激元辅助电催化剂, 光电效应, 光热效应, 硝酸根还原反应

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

陈振霖, 薛静, 武磊, 党昆, 籍宏伟, 陈春城, 章宇超, 赵进才. 协同光电及热效应实现铜光阴极上等离激元催化高效硝酸根还原反应[J]. 催化学报, 2024, 62: 219-230.

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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图/表 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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协同光电及热效应实现铜光阴极上等离激元催化高效硝酸根还原反应

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

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