机械法制备石墨二炔并耦合CdSe纳米粒子高效光催化制氢

doi:10.1016/S1872-2067(21)64053-6

摘要/Abstract

摘要：

石墨炔(GDY)独特的结构优势使其具有理想的吸光性和导电性, 较好的透光性、导电性、较高的载流子迁移率、热导率等. 与无带隙的石墨烯相比, GDY带隙为‒0.46‒1.32eV, 因此在电子、催化、光学和机械方面具有较大的应用潜力, 引起了研究人员的广泛关注.

本文以六卤苯(C₆Br₆)与碳化钙(CaC₂)为主要原料, 乙酸铜和Pb(PPh₃)₄为催化剂, 采用简单的球磨机械力化学耦合法, 使前驱体C₆Br₆和CaC₂在催化剂的作用下在球磨反应中耦联, 然后在惰性气体氛围中煅烧去除未完全反应的前驱体, 再使用强酸将催化剂去除, 最终得到了高纯度的GDY. 利用X射线衍射、扫描电子显微镜、透射电子显微镜、X射线光电子能谱、傅立叶变换红外光谱和拉曼光谱等对制得的GDY进行表征, 结果表明成功制得了GDY. 将GDY与CdSe纳米粒子耦合, 构建了GDY/CdSe 2D/0D异质结, 并将其应用于光催化析氢反应. GDY独特的二维(2D)结构为CdSe纳米粒子提供了分散平台, 有效阻止了CdSe纳米粒子的团聚. 稳态瞬态荧光测试结果表明, CdSe与GDY耦合形成的复合催化剂被光激发后产生的瞬态荧光由激发态回到基态的时间大大缩短, 这表明复合催化剂光激发产生的电子-空穴对通过催化剂间异质结形成的电子转移通道迅速转移, 并参与析氢反应. 在瞬态光电流测试中, GDY/CdSe-20(CdSe与GDY质量比为20%)复合催化剂的光响应强度最大, 且GDY/CdSe-20具有较低的析氢过电位, 有利于析氢反应进行. 此外, 电化学阻抗测试结果表明, GDY具有良好的导电性, 可以快速有效地将CdSe中产生的光电子转移到析氢反应中. 复合催化剂GDY/CdSe-20的析氢活性为6470 μmol g^‒1 h^‒1, 分别是纯GDY(14 μmol g^‒1 h^‒1)和纯CdSe(157 μmol g^‒1 h^‒1)的462倍和41倍. 利用原位X射线光电子能谱分析光照前后各元素的结合能, 考察了各元素周围电子云密度变化, 并推测光电子的转移路径, 提出了可能的析氢反应机理. 综上, 本文利用机械球磨法制备了石墨二炔, 简化了GDY的制备方案, 为大规模制备GDY提供了参考.

关键词: 石墨炔, 机械球磨, 碳化钙, 六卤苯, 析氢

Abstract:

Graphdiyne (GDY) has attracted considerable attention as a new two-dimensional (2D) carbon hybrid material because of its good conductivity, adjustable electronic structure, and special electron transfer enhancement properties. GDY has great potential in the field of photocatalytic water splitting for hydrogen evolution, owing to its unique properties. In this study, GDY was successfully prepared by the mechanochemical coupling of precursors C₆Br₆ and CaC₂ using a ball-milling approach. The prepared GDY, especially its microstructure and composition, was well characterized using different techniques such as X-ray diffraction, scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), Fourier-transform infrared, and Raman characterization techniques. By exploiting the unique two-dimensional (2D) structure and outstanding light absorption properties of GDY, GDY/CdSe 2D/0D heterojunctions were successfully established and applied to photocatalytic hydrogen evolution. The hydrogen evolution activity of GDY/CdSe-20, a type of composite material, reached 6470 μmol g^-1 h^-1, which is 461 and 40 times higher than that of GDY and CdSe, respectively. Moreover, the fine electrical conductivity of GDY enabled rapid and effective transfer of the photogenerated electrons in CdSe into the hydrogen evolution reaction. The transfer path of the photogenerated electrons was studied through XPS with in situ irradiation, and a reasonable mechanism for the hydrogen evolution reaction was proposed. This study provides a feasible approach for the large-scale preparation of GDY and demonstrates the prospects of GDY in the field of photocatalysis.

Key words: Graphdiyne, Mechanical ball-milling, CaC₂, C₆Br₆, Hydrogen evolution

范召博, 郭鑫, 杨梦雪, 靳治良. 机械法制备石墨二炔并耦合CdSe纳米粒子高效光催化制氢[J]. 催化学报, 2022, 43(10): 2708-2719.

Zhaobo Fan, Xin Guo, Mengxue Yang, Zhiliang Jin. Mechanochemical preparation and application of graphdiyne coupled with CdSe nanoparticles for efficient photocatalytic hydrogen production[J]. Chinese Journal of Catalysis, 2022, 43(10): 2708-2719.

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链接本文: https://www.cjcatal.com/CN/10.1016/S1872-2067(21)64053-6

https://www.cjcatal.com/CN/Y2022/V43/I10/2708

图/表 13

Scheme 1. Synthesis of GDY, CdSe, and GDY/CdSe-x.

Fig. 1. XRD patterns of CdSe and GDY (a), GDY/CdSe-5, GDY/CdSe-10, GDY/CdSe-15, GDY/CdSe-20 and GDY/CdSe-25 (b). (c) FTIR patterns of CdSe, GDY, GDY/CdSe-20. (d) Raman spectrum of GDY.

Fig. 2. SEM images of GDY (a), CdSe (b), GDY/CdSe-20 (c). (d) TEM images of GDY/CdSe-20. (e) HRTEM image of GDY/CdSe-20. (f) EDX image of GDY/CdSe-20. (g) Elemental mapping of GDY/CdSe-20.

Fig. 3. XPS patterns: (a) full-scan spectra of CdSe, GDY, GDY/CdSe-20; (b) C 1s spectra of GDY, GDY/CdSe-20; Cd 3d (c) and Se 3d (d) spectra of CdSe, GDY/CdSe-20.

Fig. 4. N2 adsorption isotherm (a) and pore size distribution (b) of CdSe, GDY, and GDY/CdSe-20.

Table 1 Specific physical adsorption performance parameters of CdSe, GDY, and GDY/CdSe-20.

Sample	A_BET (m² g^-1)	Pore volume (cm³ g^-1)	Average pore size (nm)
CdSe	69	0.17	8
GDY	172	0.47	13
GDY/CdSe-20	120	0.28	10

Fig. 5. (a) UV-vis DRS profiles of GDY, CdSe, GDY/CdSe-5, GDY/CdSe-10, GDY/CdSe-15, GDY/CdSe-20, and GDY/CdSe-25. (b) Corresponding plots of (αhν)1/2 versus hν for CdSe and VB-XPS spectrum of GDY (inset).

Fig. 6. (a,b) H2 production activity of GDY, CdSe, and GDY/CdSe-x composite catalyst. (c) H2 evolution with GDY/CdSe-20 within 5 h using di?erent sacrificial agents. (d) Stability data for GDY/CdSe-20. SEM (e) and XRD (f) images of GDY/CdSe-20 after hydrogen evolution cyclic reaction.

Table 2 Comparison of documented photocatalytic hydrogen production rates with that of GDY/CdSe-20.

Photocatalyst	Sacrificial reagent	Light source	HER (μmol g^-1 h^-1)	Ref.
GDY/CdSe	Na₂S/Na₂SO₃	5 W LED (λ ≥ 420)	6374	This work
TF-g-C₃N₄/CdSe	Na₂S/Na₂SO₃	400 W lamp (λ ≥ 420)	6200	[60]
CeO₂/CdSe	Na₂S/Na₂SO₃	300 W lamp (λ ≥ 300)	283	[61]
CdSe/rGO/g-C₃N₄	ascorbic acid	500 W lamp (λ ≥ 400)	1435	[62]
CdS/GDY	triethanolamine	5 W LED (λ ≥ 450)	820	[63]
NiAl-LDH/GDY	triethanolamine	5 W LED (λ ≥ 420)	649	[64]
GD-CuI-NiTiO₃	triethanolamine	5 W LED (λ ≥ 420)	509	[65]

Fig. 7. PL (a) and TRPL (b) spectra of CdSe and GDY/CdSe-20.

Table 3 Decay parameters of pure CdSe catalyst and composite GDY/CdSe-20 catalyst.

Photocatalyst	τ₁ [ns] (B₁)	τ₂ [ns] (B₂)	τ₃ [ns] (B₃)	τ_av [ns]	χ²
CdSe	5.08 (33.94 %)	14.87 (35.97%)	0.90 (30.09%)	2.48	1.61
GDY/CdSe-20	4.58 (35.08%)	13.97 (33.08%)	0.62 (31.84%)	1.69	1.77

Fig. 8. (a) Photocurrent response. (b,c) EIS. (d) LSV curves of GDY, CdSe, and GDY/CdSe-20. (e,f) Mott-Schottky plots of CdSe and GDY.

Fig. 9. (a) Schematic illustration of charge transfer process at 0D/2D CdSe/GDY heterojunction. (b) Band structure of CdSe and GDY and electron transfer model for photocatalytic hydrogen evolution.

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