The preparation and use of γ-graphdiyne, a superb new photoelectrocatalyst
摘要: γ-石墨双炔（γ-graphdiyne，简称GDY）是一种由sp和sp2杂化碳组成的高度共轭全碳材料，其独特的有序孔道、非均匀的电子结构和易于调谐的本征带隙，为制备高活性光电催化剂开辟了广阔的探索空间。本文总结了GDY的特性，合成策略和在光电催化领域中的应用，并给出了目前研究中存在的问题和未来技术发展的可能方向。Abstract: Photoelectrocatalysis is a sustainable process that plays a central role in clean energy production and pollution removal. Due to the constraints of current photoelectrocatalysts such as instability and scarcity, scientists have resorted to carbon nanomaterials that are more stable and abundant. It has been found that γ-graphdiyne (GDY), the most stable carbon phase among graphynes that contains a diacetylene bond, has some striking properties such as well-ordered pores, non-uniform electronic structure, easily tunable bandgap and excellent photoelectric performance. It has become a new “star” as a highly active photoelectrocatalyst. Its properties, synthesis strategies and photoelectrocatalytic applications are reviewed. Five reaction systems are summarized based on the phase state of the precursors and catalysts, which include liquid-solid, liquid-liquid, gas-liquid, gas-solid, and solid-gas systems. The roles GDY play in photoelectrocatalysis itself, or as a support for single atom catalytic species are discussed. Problems for current research work are discussed and future research trends are proposed.
Figure 6. Growth on Cu substrates:(a) schematic diagram of coupling reaction on Cu substrates, (b) the optical image and (c) the SEM image of GDY, (d) the profile of the GDY film height by AFM, (e) Raman spectra of the GDY film on three positions and (f) nnarrow scan for element C by XPS. Reprinted with permission.
Figure 7. (a) SEM images of the formation process of GDY nanowalls in time series (from left to right, respectively): bare Cu plate before reaction and 8 and 10 h after reaction. (b) SEM images of GDY on Cu substrate from a cross-sectional view. (c) AFM image of an exfoliated sample on Si/SiO2 substrate. (d) Schematic presentation of the synthesis process of GDY through graphene template method. (e) Nitrogen adsorption–desorption isotherms of GDY grown on graphene (red, GDY/G) and GDY. Reprinted with permission.
Figure 8. Arbitrary substrate method. (a) schematic illustration of the experimental setup about synthesis of GDY nanowalls on arbitrary substrates via copper envelope catalysis, SEM morphology of (b) 1D Si nanowires, (c) 2D Au foil and (d) 3D graphene foam and (e) schematic illustration of the fabrication of GDY on arbitrary substrates with the controlled-release method and the photos of the fabricating process on the glass and silica gel substrates. Reprinted with permission.
Figure 9. Liquid/liquid interface assisted method. (a) schematic illustration, (b) photograph of experiment, (c) AFM image of the as-prepared GDY film and (d) SAED pattern of the as-prepared GDY film. Reprinted with permission.
Figure 10. Gas-liquid interface assisted synthesis. (a) schematic diagram, (b) AFM image of the as-prepared GDY nanosheets and (c) diagonal and horizontal plots from the 2D grazing incidence wide-angle X-ray scattering (2D GIWAXS) pattern (Orange line, diagonal plots; blue line, horizontal plots). Reprinted with permission.
Figure 11. Chemical vapor deposition method. (a) experimental setup of the CVD system for the growth of linked carbon monolayer on silver surface using HEB as a precursor, (b) AFM image of GDY film (thickness: 0.6 nm), (c) TEM image and corresponding SAED pattern of GDY film, (d) Raman spectra of the as-grown ten-layer GDY, (e) high-resolution asymmetric C 1s XPS spectrum of GDY. Reprinted with permission.
Figure 12. Explosion approach. (a) schematic illustration, SEM images of GDY powder with different morphologies, (b) GDY nanoribbons, (c) GDY nanochain and (d) 3D GDY framework, and (e) their Raman spectra. Reprinted with permission.
Figure 14. (a) Schematic diagram of the photoelectrochemical cell consisting of the assembled CdSe QDs/GDY photocathode, and corresponding interfacial migration process of the photogenerated excitons, (b) LSV scanning from 0.3 to 0.4 V at 2 mV s-1 with light off (black trace) and on (red trace) for the CdSe QDs/GDY photocathode, (c) controlled potential electrolysis of the CdSe QDs/GDY photocathode during 12 h test, (d) schematic representation of the BiVO4/GDY composite used as a photoanode and its TEM image, (e) hole injection yield of BiVO4 and GDY/BiVO4 photoanodes and (f) linear sweep voltammetry scanning for different photocathodes measured under dark and light. Reprinted with permission.
Figure 15. (a) Schematic illustration for the possible mechanism of ORR for the NGDY catalyst, (b) top view of the optimized configuration for Fe atom adsorption on GDY (Atomic color code: pale blue that is for carbon in the C6 ring with sp2 hybridization, green for carbon in the acetylenic-like rods with sp hybridization and orange for Fe), (c) indicative of single Fe atom anchored on a GDY surface, (d) CV responses of the Fe/GDY catalyst (upper panel) and the commercial Pt/C catalyst (lower panel) in N2- (blue line) and O2-saturated (red line) 0.1 mol L−1 KOH solution at ambient temperature and (e) RDE measurements in O2-saturated 0.1 mol L KOH solution for the Fe/GDY catalyst (orange), and the commercial 20wt% Pt/C catalyst (violet). Reprinted with permission.
Figure 16. (a) Schematic illustration, Tafel plot at a sweep rate of 5 mV/s, and HER polarization curve of Cu@GDY/CF, (b) HER polarization curves of CoNC/GD and commercial Pt/C (10 wt%) before and after 36000 and 8000 CV scans, respectively, in 1 mol L−1 KOH and (c) before and after 9000 and 8000 CV scans, respectively, in 1 mol L−1 PBS (pH=7), (d) per mass activities of Ni/GD, Fe/GD, and Pt/C (inset: mass activities obtained at overpotentials of 0.05 and 0.20 V), (e) per mass activities of Pd(0)/GDY and Pt/C (inset: mass activity collected at overpotentials of 0.05 and 0.2 V) and (f) corresponding Tafel slopes of several catalysts including Pd(0)/GDY. Reprinted with permission.
Figure 17. (a) Schematic diagram of the 3D Cu@GDY/Co electrode, (b) LSV curves for the Cu foam, Cu@GDY, and Cu@GDY/Co electrodes in 0.1 mol L−1 KOH, (c) tafel plots of the corresponding electrodes, (d) a comparison of CoAl-LDH (CO32-) assembled hydrophobic and superhydrophilic GDY electrodes, (e) required overpotential to reach 10 mA·cm-2 of the different samples and (f) Tafel plots of the different samples. Reprinted with permission.
Table 1. A brief summary for the calculated bond lengths of GDY (nm).
Aromatic Single Triple Note 0.1407 0.1395a, 0.1340b 0.1263 MD, AIREBD 0.1405 0.1396a, 0.1340b 0.1240 MD, AIREBO potential 0.1440 0.1400a, 0.1341b 0.1239 DFT, GGA-PBE 0.1431 0.1395a, 0.1337b 0.1231 VASP, GGA-PBE a: C(sp2)-C(sp), b: C(sp)-C(sp).
* The typical lengths for aromatic bond and single bond are about 0.140 and 0.154 nm.
Table 2. Intrinsic hole/electron mobilities (300 K) and bandgap of Si, monolayer GDY and GR.
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