分形等离激元黑金的热电子催化性能

doi:10.7503/cjcu20200092

摘要/Abstract

摘要：

借鉴电镀工业中过电流“烧焦”现象, 在过电流沉积条件下一步制备出等离激元黑金. 扫描电子显微镜、透射电子显微镜、 X射线衍射和紫外-可见-近红外吸收光谱等表征结果显示, 该黑金是具有三维分形结构的多晶纳米金, 可以在 400~1800 nm宽波段范围内吸收光. 电催化甲醇结果显示, 黑金在宽波长光照下可以将甲醇的电催化效率提高 15.2%, 其主要贡献来源于等离激元生成的热电子, 而一小部分来自环境热. 在不同的单色光照条件下, 黑金的催化效率差别不大, 表明其对光能的利用没有明显的波长选择性.

关键词: 等离激元, 黑金, 宽波段吸收, 热电子, 光催化

Abstract:

This study takes the advantage of the overcurrent “burning” phenomenon in electroplating industry to prepare plasmonic black gold using one-step overcurrent electrodeposition. The characterization results of scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and ultraviolet-visible-near infrared absorption spectroscopy reveal that the black gold shows a three-dimensional fractal nanostructure composed of polycrystalline gold, which can absorb light over a broad-band range of 400—1800 nm. The results of methanol electrocatalytic oxidation show that the overall electrocatalytic efficiency of the black gold can be enhanced by 15.2% under light illumination from a Xe lamp, suggesting good hot electron catalytic activity. The improvement of the catalytic performance is mainly contributed to the plasmon-generated hot electrons, with minor contribution from the increased temperature. Under monochromatic light illumination with different wavelengthes, the black Au shows no obvious variation in the catalytic efficiency, suggesting its light utilization capability has no apparent dependence on the wavelength of the illumination light.

Key words: Plasmon, Black gold, Broad band absorption, Hot electron, Photocatalysis

中图分类号:

O644

TrendMD:

余仁鹏, 韩梅, 张梦瑶, 刘建芳, 李末霞, 胡家文. 分形等离激元黑金的热电子催化性能. 高等学校化学学报, 2020, 41(7): 1638.

YU Renpeng, HAN Mei, ZHANG Mengyao, LIU Jianfang, LI Moxia, HU Jiawen. Fractal, Plasmonic Black Gold for Hot Electron Catalysis^†. Chem. J. Chinese Universities, 2020, 41(7): 1638.

图/表 6

Fig.1 SEM images(A—C) of the B-Au with different magnifications, HRTEM image of a single B-Au particle(D) and EDS spectrum(E) and XRD pattern(F) of the B-Au

Fig.2 Reflection spectra and photograph(inset) of the B-Au and flat Au(A) and T-t curves and corresponding infrared thermal image(inset) of the B-Au and flat Au illuminated by a Xenon lamps(100 mW /cm2)(B)

Fig.3 CV curves for B-Au and flat Au in 0.5 mol/L H2SO4 solution(A) and 0.5 mol/L methanol+1.0 mol/L KOH solution(B) at a scan rate of 50 mV/s, CV curves at different scan rates(C) and plot of the current versus scan rate at 0.66 V(D) of B-Au in 0.5 mol/L H2SO4 solution

Fig.4 j-t curve of the B-Au illuminated with intermittent light from a Xe lamp(100 mW/cm2 )(A), CVs for the B-Au in 0.5 mol/L methanol + 1.0 mol/L KOH solution at a scan rate of 50 mV/s without and with light illumination(100 mW/cm2) for different duration(B), changes in peak current over time [the circled part in panel(B)](C), and j-t curves for the B-Au polarized at 0.1 V(vs. SCE) in 0.5 mol/L methanol+1.0 mol/L KOH with and without light illumination(100 mW/cm2)(D)

Fig.5 j-t curves for B-Au without light illumination(at different temperatures) and with continuous light illumination for 20 min(100 mW/cm2)(A), CVs for the B-Au without light illumination(27 ℃), with instant light illumination(27 ℃), and with continuous light illumination for 20 min(scan rate: 50 mV/s)(B), magnification of the oxidation peaks from panel(B)(C) and effect of excitation wavelength on the peak current(D) All these experiments were performed in 0.5 mol/L methanol+1.0 mol/L KOH solution.

Fig.6 Schematic illustration of the chemical reaction and possible charge transfer channels of the hot electrons in the B-Au The dashed black and red lines represent the location of the energy level of the hot holes(Eh) and the Fermi level(Ef), respectively.

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