As a fascinating conjugated polymer, graphitic carbon nitride (g-C3N4) has become a new research hotspot and drawn broad interdisciplinary attention as a metal-free and visible-light-responsive photocatalyst in the arena of solar energy conversion and environmental remediation. This is due to its appealing electronic band structure, high physicochemical stability, and "earth-abundant" nature. This critical review summarizes a panorama of the latest progress related to the design and construction of pristine g-C3N4 and g-C3N4-based nanocomposites, including (1) nanoarchitecture design of bare g-C3N4, such as hard and soft templating approaches, supramolecular preorganization assembly, exfoliation, and template-free synthesis routes, (2) functionalization of g-C3N4 at an atomic level (elemental doping) and molecular level (copolymerization), and (3) modification of g-C3N4 with well-matched energy levels of another semiconductor or a metal as a cocatalyst to form heterojunction nanostructures. The construction and characteristics of each classification of the heterojunction system will be critically reviewed, namely metal-g-C3N4, semiconductor-g-C3N4, isotype g-C3N4/g-C3N4, graphitic carbon-g-C3N4, conducting polymer-g-C3N4, sensitizer-g-C3N4, and multicomponent heterojunctions. The band structures, electronic properties, optical absorption, and interfacial charge transfer of g-C3N4-based heterostructured nanohybrids will also be theoretically discussed based on the first-principles density functional theory (DFT) calculations to provide insightful outlooks on the charge carrier dynamics. Apart from that, the advancement of the versatile photoredox applications toward artificial photosynthesis (water splitting and photofixation of CO2), environmental decontamination, and bacteria disinfection will be presented in detail. Last but not least, this comprehensive review will conclude with a summary and some invigorating perspectives on the challenges and future directions at the forefront of this research platform. It is anticipated that this review can stimulate a new research doorway to facilitate the next generation of g-C3N4-based photocatalysts with ameliorated performances by harnessing the outstanding structural, electronic, and optical properties for the development of a sustainable future without environmental detriment.
Opening up a band gap and finding a suitable substrate material are two big challenges for building graphene-based nanodevices. Using state-of-the-art hybrid density functional theory incorporating long-range dispersion corrections, we investigate the interface between optically active graphitic carbon nitride (g-C(3)N(4)) and electronically active graphene. We find an inhomogeneous planar substrate (g-C(3)N(4)) promotes electron-rich and hole-rich regions, i.e., forming a well-defined electron-hole puddle, on the supported graphene layer. The composite displays significant charge transfer from graphene to the g-C(3)N(4) substrate, which alters the electronic properties of both components. In particular, the strong electronic coupling at the graphene/g-C(3)N(4) interface opens a 70 meV gap in g-C(3)N(4)-supported graphene, a feature that can potentially allow overcoming the graphene's band gap hurdle in constructing field effect transistors. Additionally, the 2-D planar structure of g-C(3)N(4) is free of dangling bonds, providing an ideal substrate for graphene to sit on. Furthermore, when compared to a pure g-C(3)N(4) monolayer, the hybrid graphene/g-C(3)N(4) complex displays an enhanced optical absorption in the visible region, a promising feature for novel photovoltaic and photocatalytic applications.
We demonstrated for the first time by large-scale ab initio calculations that a graphene/titania interface in the ground electronic state forms a charge-transfer complex due to the large difference of work functions between graphene and titania, leading to substantial hole doping in graphene. Interestingly, electrons in the upper valence band can be directly excited from graphene to the conduction band, that is, the 3d orbitals of titania, under visible light irradiation. This should yield well-separated electron-hole pairs, with potentially high photocatalytic or photovoltaic performance in hybrid graphene and titania nanocomposites. Experimental wavelength-dependent photocurrent generation of the graphene/titania photoanode demonstrated noticeable visible light response and evidently verified our ab initio prediction.
The {010} and {110} crystal facets of monoclinic bismuth vanadate (m-BiVO4) has been demonstrated to be the active reduction and oxidation sites, respectively. Here, we show using dual-faceted m-BiVO4 with distinctly different dominant exposed facets, one which is {010}-dominant and the other {110}-dominant, contrary to prediction, the former m-BiVO4 exhibits superior photooxidation activities. The population of photogenerated electrons and holes on the surface are revealed to be proportional to the respective surface areas of {010} and {110} exposed on m-BiVO4, as evidenced by steady-state photoluminescence (PL) measurements in the presence of charge scavengers. The better photoactivity of {010}-dominant m-BiVO4 is attributed to prompt electron transfer facilitated by the presence of more photogenerated electrons on the larger {010} surface. Additionally, the greater extent of electron trapping in {110}-dominant m-BiVO4 also deteriorates its photoactivity by inducing electron-hole pair recombination.
This review summarises the recent advances of various strategies in improving the performances of BiVO4 in photocatalytic and photoelectrochemical systems.
Au-Ni core-shell nanorods (NRs) and Au-Pt-Ni core-sandwich-shell NRs are synthesized and exhibit high activity for selective H O production via direct oxygen reduction. The epitaxial growth with coherent lattice fringes allow for the tuning of the oxygen reduction pathway. Moreover, a selectivity of 95% and mass activity of 192.9 A g are achieved using Au-Pt-Ni NRs at 150 mV overpotential.
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