Chlorine intercalation in graphitic carbon nitride for efficient photocatalysis
TL;DR: In this article, a chlorine intercalated mesoporous metal-free graphitic carbon nitride (g-C3N4) was used for photocatalytic applications.
Abstract: Metal-free graphitic carbon nitride (g-C3N4) shows tremendous potentials in energy and environmental domains. Nonetheless, amelioration on the crystal configuration, electronic structure and microstructure of g-C3N4 for high-performing visible-light photocatalysis is still challenging and anticipated. Here we report the development of chlorine (Cl) intercalated g-C3N4 via co-pyrolysis of melamine and excessive ammonium chloride (excessive is very pivotal). This protocol renders not only Cl intercalation in the interlayer of g-C3N4, but also a homogeneous porous structure, thereby endowing g-C3N4 with multiple superiority effects, including significantly promoted charge migration by establishing interlayer pathway, up-shifted conduction-band level, narrowed band gap as well as enhanced surface area. The as-prepared Cl intercalated mesoporous g-C3N4 parades outstanding photocatalytic performance for water splitting into H2, CO2 reduction, liquid and air contaminants removal. The most enhanced photocatalytic performance was obtained at Cl-C3N4-3 for H2 evolution activity, which shows a 19.2-fold increase in contrast to pristine g-C3N4, accompanying with a high apparent quantum efficiency of 11.9% at 420 ± 15 nm. Experimental and DFT calculations results co-disclose that the aforementioned advantageous factors account for the profoundly boosted photooxidation and photoreduction capabilities of g-C3N4 under visible light. The present work may furnish a bottom-up tactic for integrally advancing g-C3N4, and also hold huge promise to be extended to other layered materials for photochemical or photoelectrochemical applications.
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TL;DR: Various cocatalysts, such as the biomimetic, metal-based,Metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area.
Abstract: Photoreduction of CO2 into sustainable and green solar fuels is generally believed to be an appealing solution to simultaneously overcome both environmental problems and energy crisis. The low selectivity of challenging multi-electron CO2 photoreduction reactions makes it one of the holy grails in heterogeneous photocatalysis. This Review highlights the important roles of cocatalysts in selective photocatalytic CO2 reduction into solar fuels using semiconductor catalysts. A special emphasis in this review is placed on the key role, design considerations and modification strategies of cocatalysts for CO2 photoreduction. Various cocatalysts, such as the biomimetic, metal-based, metal-free, and multifunctional ones, and their selectivity for CO2 photoreduction are summarized and discussed, along with the recent advances in this area. This Review provides useful information for the design of highly selective cocatalysts for photo(electro)reduction and electroreduction of CO2 and complements the existing reviews on various semiconductor photocatalysts.
1,365 citations
TL;DR: In this article, a novel CD modified Z-scheme photocatalyst (CDs/g-C3N4/MoO3) was successfully constructed and the morphologies, chemical compositions, and optical properties of the prepared catalysts were investigated via a series of characterization techniques.
Abstract: Carbon quantum dots (CDs) have been frequently used for broadening spectrum light response due to their superior up-conversion photoluminescence (UPPL) property and effective charge separation capacity. In this study, a novel CDs modified Z-scheme photocatalyst (CDs/g-C3N4/MoO3) was successfully constructed. The morphologies, chemical compositions, and optical properties of the prepared catalysts were investigated via a series of characterization techniques. Systematic studies indicated that the CDs/g-C3N4/MoO3 photocatalyst exhibited remarkably enhanced visible-light photocatalytic activity for the degradation of tetracycline (TC) compared to pristine g-C3N4 and MoO3/g-C3N4 composite. Doping 0.5% CDs resulted in the highest TC degradation rate, which was 3.5 and 46.2 times higher than that of MoO3/g-C3N4 and g-C3N4, respectively. The enhanced photocatalytic performance of CDs/g-C3N4/MoO3 can be attributed to the synergistic effects of CD properties (i.e., excellent UPPL activity and high charge separation capacity and the Z-scheme heterojunction structure). Reactive species scavenging experiments revealed that photogenerated holes are the main active species during the photocatalytic process. Possible photocatalytic degradation pathways of TC were proposed through the identification of intermediates using HPLC-MS and the frontier electron density calculation. Experimental results showed that the newly fabricated Z-scheme CDs/g-C3N4/MoO3 is a promising photocatalyst for the removal of TC from the environment.
605 citations
TL;DR: In this paper, a 3D mesoporous ultrathin g-C 3 N 4 photocatalyst with superior photocatalytic performance compared to conventional calcination-derived gC 3N 4 is presented.
557 citations
TL;DR: In this paper, a metal-free carbon doping-carbon nitride (BCM-C 3 N 4 ) nanocomposite was synthesized by introducing barbituric acid and cyanuric acids during the polymerization of melamine.
Abstract: Many organic and inorganic compounds have been developed as visible light driven photocatalysts for environment and energy application. In this work, a metal-free carbon doping–carbon nitride (BCM-C 3 N 4 ) nanocomposite was synthesized by introducing barbituric acid and cyanuric acid during the polymerization of melamine. The BCM-C 3 N 4 was characterized by structure, porosity, optical performance, and photoelectrochemical properties. Results demonstrated that BCM-C 3 N 4 sample exhibited higher surface area, lower fluorescence intensity, better photocurrent signals and more efficient charge transfer in comparison to pure C 3 N 4 . The BCM-C 3 N 4 exhibits excellent photocatalytic degradation ability of sulfamethazine (SMZ) under visible light irradiation. Much superior photocatalytic activity and high pollutant mineralization rate was achieved by BCM-C 3 N 4 , where it was 5 times than that of pristine C 3 N 4 . The effect of initial SMZ concentrations on photocatalyst was also investigated. Additionally, the trapping experiments and electron spin resonance tests demonstrated that the main active species, such as O 2 − and h + , could be produced under light irradiation. This work might provide an effective approach to the design of low-cost and highly efficient photocatalysis degradation systems for water treatment.
458 citations
TL;DR: In this article, the basic concepts and principles of photocatalytic water splitting have been discussed, and a guide for the selection of appropriate photocatalyst, focusing on the g-C3N4 nanomaterials, has been proposed.
Abstract: Graphitic carbon nitride (g-C3N4) is a metal-free conjugated polymer constructed from two-dimensional sheets with a bandgap energy of 2.7 eV, which makes it an applicable and efficient visible-active photocatalyst for H2 production. In the present study, the basic concepts and principles of photocatalytic water splitting have been discussed, and a guide for the selection of appropriate photocatalysts, focusing on the g-C3N4 nanomaterials, has been proposed. Our approach is mainly concentrated on evaluating two factors, namely the solar-to-hydrogen (STH) conversion and apparent quantum yield (AQY) for different photocatalysts, to provide an in-depth analysis and a framework for solar H2 production for future research directions. We compared hydrogen production from an economic viewpoint and performance of g-C3N4 nanomaterials through photochemical (PC) and photoelectrochemical (PEC) methods. Various approaches for efficient solar H2 generation over a modified g-C3N4 surface with the possibility for commercialization have been introduced. The promising approaches for the effective utilization of g-C3N4 are categorized into three proposed methods: electronic structure tuning, hybrid and nanocomposite fabrication, and finally geometric structure manipulation. Finally, we compared the recent findings and key achievements for g-C3N4-based photocatalysts modified based on the abovementioned three approaches to propose two possible scenarios for their use in the future development of efficient solar H2 generation.
432 citations
References
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TL;DR: A simple derivation of a simple GGA is presented, in which all parameters (other than those in LSD) are fundamental constants, and only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked.
Abstract: Generalized gradient approximations (GGA’s) for the exchange-correlation energy improve upon the local spin density (LSD) description of atoms, molecules, and solids. We present a simple derivation of a simple GGA, in which all parameters (other than those in LSD) are fundamental constants. Only general features of the detailed construction underlying the Perdew-Wang 1991 (PW91) GGA are invoked. Improvements over PW91 include an accurate description of the linear response of the uniform electron gas, correct behavior under uniform scaling, and a smoother potential. [S0031-9007(96)01479-2] PACS numbers: 71.15.Mb, 71.45.Gm Kohn-Sham density functional theory [1,2] is widely used for self-consistent-field electronic structure calculations of the ground-state properties of atoms, molecules, and solids. In this theory, only the exchange-correlation energy EXC › EX 1 EC as a functional of the electron spin densities n"srd and n#srd must be approximated. The most popular functionals have a form appropriate for slowly varying densities: the local spin density (LSD) approximation Z d 3 rn e unif
146,533 citations
TL;DR: This work reviews the historical development of Transition metal dichalcogenides, methods for preparing atomically thin layers, their electronic and optical properties, and prospects for future advances in electronics and optoelectronics.
Abstract: Single-layer metal dichalcogenides are two-dimensional semiconductors that present strong potential for electronic and sensing applications complementary to that of graphene.
13,348 citations
TL;DR: It is shown that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor.
Abstract: The production of hydrogen from water using a catalyst and solar energy is an ideal future energy source, independent of fossil reserves. For an economical use of water and solar energy, catalysts that are sufficiently efficient, stable, inexpensive and capable of harvesting light are required. Here, we show that an abundant material, polymeric carbon nitride, can produce hydrogen from water under visible-light irradiation in the presence of a sacrificial donor. Contrary to other conducting polymer semiconductors, carbon nitride is chemically and thermally stable and does not rely on complicated device manufacturing. The results represent an important first step towards photosynthesis in general where artificial conjugated polymer semiconductors can be used as energy transducers.
9,751 citations
TL;DR: The basics of the suject are looked at, a brief review of the theory is given, examining the strengths and weaknesses of its implementation, and some of the ways simulators approach problems are illustrated through a small case study.
Abstract: First-principles simulation, meaning density-functional theory calculations with plane waves and pseudopotentials, has become a prized technique in condensed-matter theory. Here I look at the basics of the suject, give a brief review of the theory, examining the strengths and weaknesses of its implementation, and illustrating some of the ways simulators approach problems through a small case study. I also discuss why and how modern software design methods have been used in writing a completely new modular version of the CASTEP code.
9,350 citations
TL;DR: The homogeneous substitution of sulfur for lattice nitrogen and a concomitant quantum confinement effect are identified as the cause of this unique electronic structure and the excellent photoreactivity of C(3)N(4-x)S(x), which may shed light on general doping strategies for designing potentially efficient photocatalysts.
Abstract: Electronic structure intrinsically controls the light absorbance, redox potential, charge-carrier mobility, and consequently, photoreactivity of semiconductor photocatalysts. The conventional approach of modifying the electronic structure of a semiconductor photocatalyst for a wider absorption range by anion doping operates at the cost of reduced redox potentials and/or charge-carrier mobility, so that its photoreactivity is usually limited and some important reactions may not occur at all. Here, we report sulfur-doped graphitic C(3)N(4) (C(3)N(4-x)S(x)) with a unique electronic structure that displays an increased valence bandwidth in combination with an elevated conduction band minimum and a slightly reduced absorbance. The C(3)N(4-x)S(x) shows a photoreactivity of H(2) evolution 7.2 and 8.0 times higher than C(3)N(4) under lambda > 300 and 420 nm, respectively. More strikingly, the complete oxidation process of phenol under lambda > 400 nm can occur for sulfur-doped C(3)N(4), which is impossible for C(3)N(4) even under lambda > 300 nm. The homogeneous substitution of sulfur for lattice nitrogen and a concomitant quantum confinement effect are identified as the cause of this unique electronic structure and, consequently, the excellent photoreactivity of C(3)N(4-x)S(x). The results acquired may shed light on general doping strategies for designing potentially efficient photocatalysts.
1,762 citations