Recent progress on strategies for the preparation of 2D/2D MXene/g-C3N4 nanocomposites for photocatalytic energy and environmental applications

Abstract: Photocatalytic water splitting is an environmentally friendly technique for hydrogen production. In this work, we report a novel photocatalyst consisting of two-dimensional (2D) titanium carbide (Ti₂C) and graphitic carbon nitride (g-C₃N₄). We observe substantially enhanced water splitting activities due to the efficient synergistic interaction between Ti₂C and g-C₃N₄. Optimal properties are achieved in the g-C₃N₄ with a loading of 0.4 wt% Ti₂C with a hydrogen production rate of 47.5 μmol h⁻¹, which is 14.4 times as much as that in the case using pure g-C₃N₄, and it even outperforms Pt-loaded g-C₃N₄. We further show that the Ti₂C/g-C₃N₄ has high stability and good reproducibility. We expect that the Ti₂C/g-C₃N₄ can be a photocatalyst for large scale applications because both Ti₂C and g-C₃N₄ are low-cost, abundant, and nontoxic.

Abstract: Carbon nitride (CN) polymer is considered as a potential material for photocatalysis, but surfers from the low photoconversion efficiency due to its high defect density. Although the defects can be limited through the crystallization of CN, the photocatalytic activity of single-component photocatalyst is still restricted by the recombination of photoexcited carriers. In our work, the ordered Schottky heterojunction of heptazine-based crystalline carbon nitride (HCN) and Ti3C2 MXene was successfully prepared through ionothermal method. The HCN/Ti3C2 composites exhibit higher photocatalytic performance than pristine HCN. Particularly, the HCNT20 sample exhibits the highest photocatalytic H2 evolution activity, which is about 8 and 2 times higher than that of bulk CN and pristine HCN, respectively. The results of charge transfer dynamics and DFT calculation reveal that the photocatalytic enhancement mechanism is primarily attributed to the synergistic effects of crystallization of CN, excellent conductivity of Ti3C2 and well-constructed Schottky heterojunction.

Abstract: As one of the fascinating visible-light-responsive photocatalysts, the two-dimensional (2D) graphitic carbon nitride (g-C3N4) has drawn broad attention in the field of solar energy conversion and environmental remediation. However, intrinsic drawbacks, such as insufficient surface area, slow electron transfer and unsatisfied visible-light absorption hinder its promising applications. The incorporation of 2D MXenes and their derivatives into g-C3N4 is recognized as an effective approach to totally enhance their performance toward advanced photocatalysts. This work starts with a discussion of the fundamental photocatalytic mechanism over g-C3N4-based photocatalysts incorporated with MXenes and MXene derivatives. Then, we give a comprehensive overview on the main strategies for constructing such hybrid photocatalysts with a solid 2D/2D interfacial contact. Afterward, their typical applications in environmental and energy fields, including H2 generation, CO2 conversion, pollutant degradation, N2 fixation and H2O2 production, are discussed systematically. Finally, some concluding remarks and perspectives in this area are proposed.

Abstract: Over the past few decades, graphitic carbon nitride (g-C3 N4 ) has arisen much attention as a promising candidate for photocatalytic hydrogen evolution reaction (HER) owing to its low cost and visible light response ability. However, the unsatisfied HER performance originated from the strong charge recombination of g-C3 N4 severely inhibits the further large-scale application of g-C3 N4 . In this case, the utilization of cocatalysts is a novel frontline in the g-C3 N4 -based photocatalytic systems due to the positive effects of cocatalysts on supressing charge carrier recombination, reducing the HER overpotential, and improving photocatalytic activity. This review summarizes some recent advances about the high-performance cocatalysts based on g-C3 N4 toward HER. Specifically, the functions, design principle, classification, modification strategies of cocatalysts, as well as their intrinsic mechanism for the enhanced photocatalytic HER activity are discussed here. Finally, the pivotal challenges and future developments of cocatalysts in the field of HER are further proposed.

Abstract: The sustainable light can generate reduction and oxidation centers in situ through the generation of photoexcited electrons and holes in the presence of photocatalyst. However, the photoexcited electrons and holes have huge Coulombic attraction and high exciton binding energy due to the weak screening effect and dielectric properties in many low-dimensional conjugated polymers, such as carbon nitride. Reducing the exciton binding energy of carbon nitride and promoting the conversion of excitons into free charge carriers are necessary for improving the activity of photocatalytic reactions but still very challenging. Here, by introducing amino-cyano functional groups into carbon nitride, it is demonstrated that excitons can be effectively dissociated into electrons and holes by finely controlling the charge distribution of heptazine ring. It is found that carbon nitride with heptazine rings of positive charge distribution can greatly reduce the exciton binding energy to 24 from 71 meV. Compared with heptazine ring having negative charge distribution, heptazine ring with positive charge distribution can increase photocatalytic hydrogen production of carbon nitride by up to ten times. This work provides an easy way to promote the dissociation of excitons in carbon nitride by regulating the charge distribution.

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.

Abstract: 2.3. Evaluation of Photocatalytic Water Splitting 6507 2.3.1. Photocatalytic Activity 6507 2.3.2. Photocatalytic Stability 6507 3. UV-Active Photocatalysts for Water Splitting 6507 3.1. d0 Metal Oxide Photocatalyts 6507 3.1.1. Ti-, Zr-Based Oxides 6507 3.1.2. Nb-, Ta-Based Oxides 6514 3.1.3. W-, Mo-Based Oxides 6517 3.1.4. Other d0 Metal Oxides 6518 3.2. d10 Metal Oxide Photocatalyts 6518 3.3. f0 Metal Oxide Photocatalysts 6518 3.4. Nonoxide Photocatalysts 6518 4. Approaches to Modifying the Electronic Band Structure for Visible-Light Harvesting 6519

Abstract: Access to clean, affordable and reliable energy has been a cornerstone of the world's increasing prosperity and economic growth since the beginning of the industrial revolution. Our use of energy in the twenty–first century must also be sustainable. Solar and water–based energy generation, and engineering of microbes to produce biofuels are a few examples of the alternatives. This Perspective puts these opportunities into a larger context by relating them to a number of aspects in the transportation and electricity generation sectors. It also provides a snapshot of the current energy landscape and discusses several research and development opportunities and pathways that could lead to a prosperous, sustainable and secure energy future for the world.

Abstract: Currently, however, there are relatively few such atomically layered solids. [ 2–5 ] Here, we report on 2D nanosheets, composed of a few Ti 3 C 2 layers and conical scrolls, produced by the room temperature exfoliation of Ti 3 AlC 2 in hydrofl uoric acid. The large elastic moduli predicted by ab initio simulation, and the possibility of varying their surface chemistries (herein they are terminated by hydroxyl and/or fl uorine groups) render these nanosheets attractive as polymer composite fi llers. Theory also predicts that their bandgap can be tuned by varying their surface terminations. The good conductivity and ductility of the treated powders suggest uses in Li-ion batteries, pseudocapacitors, and other electronic applications. Since Ti 3 AlC 2 is a member of a 60 + group of layered ternary carbides and nitrides known as the MAX phases, this discovery opens a door to the synthesis of a large number of other 2D crystals. Arguably the most studied freestanding 2D material is graphene, which was produced by mechanical exfoliation into single-layers in 2004. [ 1 ] Some other layered materials, such as hexagonal BN, [ 2 ] transition metal oxides, and hydroxides, [ 4 ] as well as clays, [ 3 ] have also been exfoliated into 2D sheets. Interestingly, exfoliated MoS 2 single layers were reported as early as in 1986. [ 5 ] Graphene is fi nding its way to applications ranging from supercapacitor electrodes [ 6 ] to reinforcement in composites. [ 7 ] Although graphene has attracted more attention than all other 2D materials combined, its simple chemistry and the weak van der Waals bonding between layers in multilayer structures limit its use. Complex, layered structures that contain more than one element may offer new properties because they

Abstract: 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 constructi...