Rational Construction of Z‐Scheme Charge Transfer Based on 2D Graphdiyne (g‐C_nH_2n−2) Coupling with Amorphous Co₃O₄ Quantum Dots for Efficient Photocatalytic Hydrogen Generation

Abstract

A novel Co3O4 quantum dots (CQDs)/2D graphdiyne (GDY) Z‐scheme heterojunction is fabricated by cross‐coupling reaction and electrostatic self‐assembly methods. GDY with the features of 2D porous structures has not only conducted the adsorption of dye molecules but also CQDs is facile to be anchored on the surface. Additionally, the construction of Z‐scheme heterojunction is conductive to conquer the shortcomings of easy agglomeration and poor dispersion for CQDs. The maximum photocatalytic hydrogen generation rate of 1500.85 µmol h−1 g−1 is gained for 30% GDY/CQDs and display an apparent quantum efficiency of 1.37% at 475 nm, which is roughly 11‐fold and 2.8‐fold higher than the pristine GDY and CQDs, respectively. The superior photocatalytic H2 production performance would be put down to the intense synergy of Z‐scheme heterostructure and the size effect of CQDs. They dramatically enhance the separation and transport of photogenerated charge carriers. Besides, the Z‐scheme charge transfer mechanism is further verified through the results of photoluminescence. This work offers new insight into the design of GDY‐based Z‐scheme heterojunction for photocatalysis.

Graphdiyne(CnH2n‐2)‐Based NiCo LDH – Graphdiyne – CuI Double S‐Scheme Heterojunction For Efficient Photocatalytic Hydrogen Production**

“…In addition, a distinct absorption band can be observed at 2190 cm À 1 due to the stretching vibration of C�C. [35] The Raman spectrum of GDY (Figure 2F) shows two strong peaks (1363.83 cm À 1 and 1566.94 cm À 1 ) and two weak peaks (1999 cm À 1 and 2178 cm À 1 ). The two strong peaks are attributed to the respiration vibration of the sp 2 carbon domain of the aromatic ring (D band) structure (1363.83 cm À 1 ).…”

Functional Graphdiyne for Emerging Applications: Recent Advances and Future Challenges

“…The molecule (small molecules or macromolecules)-modified GDY are usually fabricated by solution blending via robust 𝜋-𝜋 interaction (e.g., ferrocene (Fc)modified GDY, [55] and hemin/GDY [56] ), and van der Waals interaction (e.g., poly(vinylidene fluoride) (PVDF)/GDY, [57] and polyvinylpyrrolidone (PVP)/GDY [58] ). The interface engineering of GDY modified by other nanostructures (0D, 1D, or 2D morphology) is also frequently employed for the construction of GDY-based heterostructures by versatile strategies, such as in situ cross-coupling reaction using HEB as a monomer (e.g., metal (Cr, Mn, Mo, W, and Re) SA/GDY, [59] and 1D Cu 0.95 V 2 O 5 nanorod (NR)@GDY [60] ), and self-assembly (e.g., Co 3 O 4 QD/GDY, [61] and MXene Ti 3 C 2 T x NS/GDYO [62] ). The schematic illustrations of the representative functional GDY nanoarchitectures [69,[88][89][90][91] are provided in Figure 2.…”

“…[143] However, the reported current density (j) of 2D GDY in HER reaction is still poor (< 0.2 A cm −2 ), mainly attributed to the relatively low intrinsic catalytic active sites. [127] In recent years, functional GDY nanoarchitectures that GDY bonds with heteroatoms to generate featured chemical bonds such as C−N, [144] C−Cu, [145] C−Pt, [146] and C−Pd bonds, [147] or hybridizes with other nanostructures, such as, 0D SAs or QDs, [61] 1D NWs, [81] and 2D NSs [148] to form a variety of heterojunctions, have shown remarkably boosted electrochemical catalytic performance. For example, in 2021, Wang et al [149] reported a sequential strategy for the co-doping of B and N heteroatoms into GDY, which showed that a certain sp-N doping could reduce the HER overpotential, and the subsequent incorporation of B atoms further enhanced the j due to the synergistic effect of chemical and electronic couplings on proton adsorption/reduction kinetics.…”

Rational Construction of Electrostatic Self‐Assembly of Metallike MoP and ZnIn2S4 Based on Density Functional Theory to Form Schottky Junction for Photocatalytic Hydrogen Production

“…In addition, the greater the absolute value of zeta potential, the better the stability of photocatalyst in solution. [34][35][36] At the same time, the larger the zeta potential is, the greater the electrostatic repulsion between particles, which results in a great inhibition on aggregation and sedimentation. Therefore, when the particles can maintain good dispersion in solution, it also indicates that they have good stability.…”