三维分等级花状Cd0.8Zn0.2S的结构调控及其光催化CO2还原

doi:10.1016/S1872-2067(20)63623-3

催化学报 ›› 2021, Vol. 42 ›› Issue (1): 131-140.DOI: 10.1016/S1872-2067(20)63623-3

三维分等级花状Cd_0.8Zn_0.2S的结构调控及其光催化CO₂还原

程蕾^a, 张岱南^a, 廖宇龙^a, 范佳杰^b, 向全军^a^,^*()

^a电子科学与工程学院, 电子科技大学电子薄膜与集成器件国家重点实验室, 四川成都610054
^b郑州大学材料科学与工程学院, 河南郑州450002

收稿日期:2020-03-06 接受日期:2020-04-24 出版日期:2021-01-18 发布日期:2021-01-18
通讯作者: 向全军
基金资助:
国家自然科学基金(51672099);国家自然科学基金(21403079);四川省科技计划资助(2019JDRC0027);中央高校基金(2017-QR-25)

Structural engineering of 3D hierarchical Cd_0.8Zn_0.2S for selective photocatalytic CO₂ reduction

Lei Cheng^a, Dainan Zhang^a, Yulong Liao^a, Jiajie Fan^b, Quanjun Xiang^a^,^*()

^aState Key Laboratory of Electronic Thin Film and Integrated Devices, School of Electronic Science and Engineering,University of Electronic Science and Technology of China, Chengdu 610054, Sichuan, China
^bSchool of Materials Science and Engineering, Zhengzhou University, Zhengzhou 450002, Henan, China

Received:2020-03-06 Accepted:2020-04-24 Online:2021-01-18 Published:2021-01-18
Contact: Quanjun Xiang
About author:^*Tel/Fax: +86-28-83207063; E-mail: xiangqj@uestc.edu.cn
Supported by:
National Natural Science Foundation of China(51672099);National Natural Science Foundation of China(21403079);Sichuan Science and Technology Program(2019JDRC0027);Fundamental Research Funds for the Central Universities(2017-QR-25)

摘要/Abstract

摘要：

近年来, 光催化CO₂还原被视为一种既能解决能源短缺又能减少温室气体, 改善人类生存环境的绿色新型技术. 然而, 由于CO₂气体的相对稳定性, 构建高催化活性和高选择性的催化体系仍然面临着巨大挑战. 锌硫镉固溶体作为一种廉价的固溶类材料, 具有吸光范围适宜、化学性质稳定以及能带结构可调控等特点, 在光催化还原CO₂的方面表现出巨大的潜力. 本文发展了一种简单的原位自组装法合成三维分等级花状结构的Cd_0.8Zn_0.2S, 主要包括Cd²⁺和Zn²⁺离子在含硫氛围下自组装成核状前体, 然后以柠檬酸钠作为形貌诱导剂进一步组装生长, 同时控制Cd²⁺/Zn²⁺摩尔比和反应时间以实现三维分等级花状Cd_0.8Zn_0.2S的合成. 结果表明, 三维分等级花状结构的Cd_0.8Zn_0.2S在光催化还原CO₂的过程中表现出优异的催化活性和稳定性. 其中, 在光照3 h后, CO产量达到41.4 μmol g^-1, 大约是相同光照条件下Cd_0.8Zn_0.2S纳米颗粒的三倍(14.7 μmol g^-1). 此外, 三维分等级花状结构的Cd_0.8Zn_0.2S在光催化过程中展现出对光催化产物CO的较高选择性(89.9%), 其中在没有任何牺牲剂或共催化剂作用下的TON为39.6. 太赫兹时域光谱(THz-TDS)表明, 这种三维分等级花状结构的Cd_0.8Zn_0.2S相较于Cd_0.8Zn_0.2S纳米颗粒更有利于对光的吸收, 从而提高对光的有效利用率. 原位漫反射傅立叶变化红外光谱表征分析揭示了三维分等级花状结构的Cd_0.8Zn_0.2S在光催化过程中表面吸附物质以及光催化还原中间体的存在及转化. 通过实验数据和理论机理预测表明, 该种三维分等级花状结构的Cd_0.8Zn_0.2S具有较高的电流密度和较好的载流子传输能力. 基于这种三维的花状结构, 使得Cd_0.8Zn_0.2S具有较大的比表面积和吸附位点, 进一步提升体系的CO₂吸附性能和光生电子的转移效率, 从而有效提高光催化CO₂还原的活性.

关键词: 花状Cd_0.8Zn_0.2S, 自组装生长, 光催化CO₂还原, 高选择性, 可见光

Abstract:

The solar-driven catalytic conversion of CO₂ to useful chemical fuels is regarded as an environmentally friendly approach to reduce the consumption of fossil fuels and mitigate the greenhouse effect. However, it is highly intriguing and challenging to promote the selectivity and efficiency of visible-light-responsive photocatalysts that favor the adsorption of CO₂ in photoreduction processes. In this work, three-dimensional hierarchical Cd_0.8Zn_0.2S flowers (C8Z2S-F) with ultrathin petals were successfully synthesized through an in-situ self-assembly growth process using sodium citrate as a morphology director. The flower-like Cd_0.8Zn_0.2S solid solution exhibited remarkable photocatalytic performance in the reduction of CO₂, generating CO up to 41.4 μmol g^-1 under visible-light illumination for 3 h; this was nearly three times greater than that of Cd_0.8Zn_0.2S nanoparticles (C8Z2S-NP) (14.7 μmol g^-1). Particularly, a comparably high selectivity of 89.9% for the conversion of CO₂ to CO, with a turnover number of 39.6, was obtained from the solar-driven C8Z2S-F system in the absence of any co-catalyst or sacrificial agent. Terahertz time-domain spectroscopy indicated that the introduction of flower structures enhanced the light-harvesting capacity of C8Z2S-F. The in situ diffuse reflectance infrared Fourier transform spectroscopy unveiled the existence of surface-adsorbed species and the conversion of photoreduction intermediates during the photocatalytic process. Empirical characterizations and predictions of the photocatalytic mechanism demonstrated that the flower-like Cd_0.8Zn_0.2S solid solution possessed desirable CO₂ adsorption properties and an enhanced charge-transfer capability, thus providing a highly effective photocatalytic reduction of CO₂.

Key words: Cd_0.8Zn_0.2S flowers, Self-assembly growth, Photocatalytic CO₂ reduction, High selectivity, Visible-light irradiation

程蕾, 张岱南, 廖宇龙, 范佳杰, 向全军. 三维分等级花状Cd_0.8Zn_0.2S的结构调控及其光催化CO₂还原[J]. 催化学报, 2021, 42(1): 131-140.

Lei Cheng, Dainan Zhang, Yulong Liao, Jiajie Fan, Quanjun Xiang. Structural engineering of 3D hierarchical Cd_0.8Zn_0.2S for selective photocatalytic CO₂ reduction[J]. Chinese Journal of Catalysis, 2021, 42(1): 131-140.

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图/表 8

Fig. 1. Morphology and phase structures of the photocatalyst. (a) Schematic of C8Z2S-F synthesis; (b) HAADF-STEM image; (c) TEM image; (d) XRD pattern; (e) SEM image; (f, g) AFM images of C8Z2S-F. The obtained C8Z2S-F was synthesized through a simple oil-bath treatment of CdCl2 and ZnCl2 (the molar ratio of Cd/Zn was 4:1) in thiourea solution with sodium citrate and NH3·H2O as structure directors at 60 °C for 3 h.

Fig. 2. Compositional characterizations and photocatalytic CO2 reduction performance of as-synthesized photocatalysts. (a) XPS spectra; (b) High resolution XPS spectra; (c) N2 adsorption-desorption isotherms (inset indicates the pore size distribution); (d) UV-vis DRS spectra (inset shows the Kubelka-Munk function vs. photon energy curves); (e) Mott-Schottky plots; (f) Schematic of the electronic band structures of the as-obtained C8Z2S-F sample; (g) Photocatalytic products of CO2 reduction detected by original chromatograms over C8Z2S-F and C8Z2S-NP samples under visible-light irradiation for 3 h; Photocatalytic activity of CO (h) and CH4 evolution (i) over C8Z2S-F and C8Z2S-NP samples under visible light irradiation. Reaction conditions: photocatalyst (0.03 g), deionized water (500 μL), Xe lamp (300 W).

Fig. 3. Optical performance of as-synthesized photocatalysts. THz-TDS transmittance (a) and THz-TDS reflectivity (b) of C8Z2S-F and C8Z2S-NP samples.

Fig. 4. Physicochemical properties and mechanism study of as-synthesized photocatalysts. CO2-TPD profiles (a) and EIS spectras (b) (inset shows the TPR curves) of C8Z2S-F and C8Z2S-NP samples; (c) Schematic of the photocatalytic reduction of CO2 by using C8Z2S-F sample as photocatalyst.

Fig. 5. The in situ DRIFTS spectra of CO2 adsorption over as-synthesized C8Z2S-F photocatalysts. Surface photocatalytic intermediates after introduction of CO2 + H2O interaction under dark (0-60 min) and 365 nm light irradiation (60-120 min) in different wavenumber ranges of 1000-1400 cm-1 (a) and 1400-2100 cm-1 (b); (c) schematic of the possible photocatalytic process during the conversion of CO2 to CO and CH4 under visible-light irradiation.

Fig. 6. Morphological characterizations of the photocatalysts. (a1-d1) SEM images; (a2-d2) HAADF-STEM images; (a3-d3) schematic of the structures of C2Z8S, C5Z5S, C8Z2S-F, and C8Z2S-NP samples.

Fig. 7. Comparison of electrochemical characterizations and photocatalytic CO2 reduction performance over a series of photocatalysts. N2 adsorption-desorption isotherms (a) (inset indicates the pore size distribution); UV-vis DRS spectra (b) (inset shows the Kubelka-Munk function vs. photon energy curves), Mott-Schottky plots (c), and EIS spectra (d) (inset presents the TPR curves) of C8Z2S-F, C5Z5S, and C2Z8S samples; Photocatalytic activity of CO (e) and CH4 evolution (f) over C8Z2S-F, C5Z5S and C2Z8S samples under visible-light irradiation. Reaction conditions: photocatalyst (0.03 g), deionized water (500 μL), Xe lamp (300 W).

Table 1 Evaluation of selective CO2 photoconversion.a

Sample	Production rate^b (μmol g^-1 h^-1)		TON ^c	Selectivity for CH₄^d (%)
Sample	CO	CH₄	TON ^c	Selectivity for CH₄^d (%)
C8Z2S-F	17.8	0.5	39.6	89.9
C5Z5S	11.0	0.3	24.4	90.2
C2Z8S	9.5	0.3	21.4	88.8
C8Z2S-NP	4.9	0.4	13	75.4

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三维分等级花状Cd_0.8Zn_0.2S的结构调控及其光催化CO₂还原

Structural engineering of 3D hierarchical Cd_0.8Zn_0.2S for selective photocatalytic CO₂ reduction

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