3D graphene/CoO and the photocatalytic properties for hydrogen evolution from water splitting under visible light irradiation
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摘要: 以新型二维材料氧化石墨烯和金属有机框架化合物ZIF-67为前驱体,通过溶剂热反应和高温焙烧过程,制备了一种三维交联石墨烯负载CoO纳米粒子(3D G/CoO)的复合催化剂材料。XRD、XPS、紫外可见漫反射、SEM和TEM等结构和形貌分析结果表明:平均粒径约为34.5 nm的CoO粒子均匀负载在三维交联石墨烯体相骨架中。三维石墨烯特有的光致热电子发射性能及两种材料间的协同作用,赋予了复合材料优异的光催化分解水制氢性能。在300 W氙灯照射下,催化分解水制氢速率为10.1 mmol·gcat−1·h−1;在520 nm波长可见光照射下,获得了7.77%的表观量子效率。催化剂循环使用5次,活性保持率为88%。此高性能可见光响应的三维复合催化剂材料的研究,对光催化领域中新型高效催化剂的开发和应用具有重要意义。Abstract: A three-dimensional cross-linked graphene (G) supported CoO nano composite (3D G/CoO) was prepared by solvothermal reaction followed by annealing at high temperature using graphene oxide and metal organic framework (ZIF-67) as precursors. The structures and morphologies of 3D G/CoO were characterized by XRD, XPS, UV-vis diffuse reflectance spectrum, SEM and TEM. The results show that CoO particles with an average particle size of ~34.5 nm are uniformly loaded on the graphene sheets. Based on the unique hot electron emission properties of 3D G, as well as the synergetic effect between the two components, 3D G/CoO nano composites exhibit excellent photocatalytic properties for hydrogen evolution from water splitting under the irradiation. Under 300 W Xenon lamp, the hydrogen production rate is 10.1 mmol·gcat−1·h−1. The apparent quantum efficiency of 7.77% is obtained at 520 nm visible light. After recycling for 5 times, the hydrogen production rate is maintained at 88%. This high-performance visible light responsive 3D photocatalyst is of great significance to the development of highly efficient catalysts in the field of photocatalysis.
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Key words:
- nano composite /
- photocatalysis /
- 3D graphene /
- hydrogen evolution from water splitting /
- visible light
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图 6 3D G/CoO及对照材料的光催化分解水制氢性能:((a), (b)) 紫外-可见光下;(c) 350 nm和520 nm波长光下;(d) 催化剂循环使用性能;((e), (f)) 3D G/CoO固体紫外吸收光谱及对应的能带结构图
α—Absorption coefficient; hν—Photon energy
Figure 6. Hydrogen production activity of 3D G/CoO and control material: ((a), (b)) Under UV-vis light; (c) Under simple wavelength light of 350 nm and 520 nm; (d) Cycling performance of catalyst; ((e), (f)) UV-vis absorbance spectra and the Kubelka-Munk transformation curves of 3D G/CoO
表 1 样品的命名
Table 1. Naming of sample
Sample GO/mL ZIF-67/mg 3D G 30 – 3D G/CoO 30 120 A-Co – 120 A-3 30 7.5 A-4 30 30 表 2 3D G/CoO材料与已报道的光催化剂的催化分解水制氢性能对比
Table 2. Comparison of hydrogen production rate between 3D G/CoO and the reported works
Catalyst Hydrogen production rate/(mmol·gcat−1·h−1) Excitation wavelength/nm Sacrificial agent Ref. TiO2/rGO-COOH 0.25 >400 − [34] TPA-CH2OH-rGO 19 369 CH3CH2OH [35] MoS2/g-C3N4 6.24×10−3 >400 − [36] TiO2/rGO 0.66 800>λ>420 TEOA [37] CdS/GO 2.31 420 CH3OH [38] N-rGO/Pyridine co-g-C3N4 3.04 >420 TEOA [39] Pt-rGO/ZnIn2S4CoPi/BiVO4 0.899 >420 CH3CH2OH [40] Ag-NaTaO3-rGO 3.95 400 Na2S, Na2SO3 [41] TiO2/Graphene 0.086 >400 Na2S, Na2SO3 [42] Co-P/Graphene 24.5 430 TEOA [43] Pt/K2La2Ti3O10 0.468 365 CH3OH [44] 3D G/CoO 10.1 520 CH3OH This work Notes: rGO-COOH—Reduced carboxyl-graphene oxide; rGO—Reduced graphene oxide; TEOA—Training and evaluation objectives annex; N-rGO—N-reduced graphene oxide; TPA—4-(N, N-diphenylamine)benzyl. 表 3 不同光照条件下3D G/CoO催化分解水制氢的表观量子效率(AQE)
Table 3. Apparent quantum efficiency (AQE) of 3D G/CoO for hydrogen production from water splitting under different irradiation conditions
Wavelength of incident light/nm Light intensity/mW AQE/% 350 1006.43 6.96 520 103.48 7.77 -
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