Two-dimensional Photocatalyst Research Articles

Twisted BiOCl Moiré Superlattices for Photocatalytic Chloride Reforming of Methane.

Solar-driven conversion of CH4 into value-added methyl chlorides and H2 with abundant chloride ions offers a sustainable CH4 reforming strategy but suffers from inefficient Cl- activation and severe e--h+ recombination in traditional photocatalysts. Herein, we demonstrate that BiOCl moiré superlattices with a 11.1° twist angle are highly efficient for photocatalytic CH4 reforming into CH3Cl and H2 with NaCl. These moiré superlattices, featuring misalignment-induced tensile strains, destabilize surface Bi-Cl bonds, facilitating a hole-mediated MvK-analogous process to activate lattice Cl into reactive •Cl for CH4 chlorination. Meanwhile, their twisted stacking configurations reinforce interlayer electronic coupling and thus accelerate out-of-plane carrier transfer. Along with surface anchoring of single-atom Pt sites for H2 evolution, the resulting Pt1/BiOCl moiré superlattices deliver a CH3Cl yield of 53.4 μmol g-1 h-1 with an impressive selectivity of 96% under visible light. This study highlights the potential of lattice engineering in two-dimensional photocatalysts to regulate structural strains and carrier dynamics for the decentralized reforming of CH4.

Novel Two-dimensional Tellurophosphates: Visible Light Photocatalysts for Water Splitting and Carbon Dioxide Reduction

Exploring efficient two-dimensional (2D) photocatalysts for solar-driven water splitting into hydrogen and oxygen is crucial for sustainable hydrogen energy production. In this study, we investigated the suitability of novel 2D tellurophosphates M2P2Te6 (M=Mg, Ca, Sr, Ba, Ra) for photocatalytic overall water splitting using density functional theory (DFT) approach. The stability of tellurophosphates was assessed based on formation energies, phonon dispersions, ab initio molecular dynamics, and elastic modulus results. These monolayers have desirable direct bandgaps (∼1.6 – 2.2 eV) for efficient light absorption, and their valence and conduction bands ideally straddle both the oxidation and reduction potential of water along with the ability to reduce CO2 to hydrocarbons or carbonaceous products. Moreover, Gibbs free energies of Hydrogen Evolution Reaction (HER) and Oxygen Evolution Reaction (OER) of tellurophosphate monolayers are also computed and display that these monolayers are viable photocatalysts under the influence of applied external potential. The tellurophosphates monolayers show strong optical absorption, with an absorption coefficient reaching up to 105 cm-1, across both the visible and UV regions of the solar spectrum, accompanied by high carrier mobility (order of 103 cm2 V-1s-1). The predicted solar-to-hydrogen efficiency of all monolayers exceeds 12%, fulfilling the criteria for commercial and economic viability in solar hydrogen production. The theoretical findings of current study imply that novel 2D tellurophosphate monolayers are promising candidates for optoelectronics, especially as photocatalysts for overall water splitting and CO2 reduction.

Graphene with suitable-size nitrogen-doped cavity being an excellent photocatalyst for proton-coupled electron transfer in water splitting

Aiming to attain porous carbon nitride photocatalysts with high specific surface area, abundant active sites, broad absorption range and effective electron-hole separation, we remove carbon rings from graphene and replace all the edge carbon atoms of the cavity with nitrogen atoms. The accurate electronic structures and exciton properties of the proposed materials are revealed by the ab initio many-body Green's function theory. Computational results show that the absorption of the designed materials can cover both the visible and the near-infrared light region. The exciton binding energies of the materials are one order of magnitude lower than those of the typical two-dimensional photocatalyst graphitic carbon nitride. Due to the formation of hydrogen bonds between pyridinic nitrogen atoms and water molecules during water splitting, the key excited-state proton-coupled electron transfer reactions are barrierless. These findings could serve as guidelines for the realization of high-performance metal-free two-dimensional photocatalysts.

Janus SnXY monolayers (X= P, As, Sb; Y[dbnd]H, CH3): A new class of two-dimensional photocatalysts for water splitting

Following the successful synthesis of NaSnAs in 2021, in the present study, a series of two-dimensional SnXY monolayers with X = P, As, Sb, and Y = H, CH3 are theoretically predicted. First principle calculations are performed to investigate the structural, electronic, mechanical, and optical properties of these materials. The results predict desirable dynamical and thermal stabilities with high mechanical strength for considered systems. It is found that all SnXY monolayers are semiconductors with a direct band-gap lying in the visible region. The values of band-gap decrease as the size of the X atom increases which indicates the dominant contribution of the X atom in the band edge positions. Employing biaxial strain leads to narrowing the electronic band-gaps and suggests a strain-tuneable band-gap character in these structures. The results also highlight high carrier mobilities along the SnXY monolayers. By virtue of possessing suitably large band gaps, well-matched band offsets, robust optical absorption within the visible spectrum, high carrier mobility, and moderate exciton binding energies, these systems are poised as prospective candidates for applications in photocatalysis. Accordingly, we have also explored the photocatalytic activity of SnPH and SnAsH monolayers toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). The calculated reaction free energy profiles demonstrate the exceptional performance of these systems in facilitating overall water splitting. This study provides a comprehensive vision of novel 2D SnXY monolayers and a new outlook for designing superior photocatalysts for water splitting.

Lamellar copper molybdate as a novel photocatalyst for the degradation of Rhodamine B

Water containing organic pollutants poses increasingly severe challenges to the clean water resources that humans rely on for survival. Photocatalysis is one of the technologies for removing organic pollutants from wastewater, which is green and has no secondary pollution. Here layered HCu1.5MoO5 photocatalyst is synthesized by wet chemistry. It is assembled from multiple stacked thin nanosheets with a thickness of ∼12.5 nm. The thin-layer structure of two-dimensional photocatalysts considerably reduces the migration distance of photo-generated charge carriers, thereby promoting efficient charge separation. In addition, it exhibits near-ultraviolet light response with the remarkable local surface plasmon resonance (LSPR) effect in the visible light region. The specific surface area and mesoporous structure of HCu1.5MoO5 are particularly advantageous for the mass transfer process of photocatalytic degradation. These characteristics enable it to effectively degrade Rhodamine B, achieving a degradation rate of 78.4 % after 120 min. The work provides a new perspective for the development of layered photocatalysts for photocatalytic degradation.

Elucidating Solvatochromic Shifts in Two-Dimensional Photocatalysts by Solving the Bethe-Salpeter Equation Coupled with Implicit Solvation Method.

Many studies have focused on tailoring the photophysical properties of two-dimensional (2D) materials for photocatalytic (PC) or photoelectrochemical (PEC) applications. To understand the optical properties of 2D materials in solution, we established a computational method that combined the Bethe-Salpeter equation (BSE) calculations with our GW-GPE method, allowing for GW/BSE-level calculations with implicit solvation described using the generalized Poisson equation (GPE). We applied this method to MoS2, phosphorene (PP), and g-C3N4 and found that when the solvent dielectric increased, it reduced the exciton binding energy and quasiparticle bandgap, resulting in almost no solvatochromic shift in the excitonic peaks of MoS2 and PP, which is consistent with previous experiments. However, our calculations predicted that the solvent dielectric had a significant impact on the excitonic properties of g-C3N4, exhibiting a large solvatochromic shift. We expect that our GW/BSE-GPE method will offer insights into the design of 2D materials for PC and PEC applications.

Harmonizing the cyano-group and Na to enhance selective photocatalytic O2 activation on carbon nitride for refractory pollutant degradation

Manipulating exciton dissociation and charge-carrier transfer processes to selectively generate free radicals of more robust photocatalytic oxidation capacity for mineralizing refractory pollutants remains challenging. Herein, we propose a strategy by simultaneously introducing the cyano-group and Na into graphitic carbon nitride (CN) to obtain CN-Cy-Na, which makes the charge-carrier transfer pathways the dominant process and consequently achieves the selective generation of free radicals. Briefly, the cyano-group intensifies the local charge density of CN, offering a potential well to attract the hole of exciton, which accelerates the exciton dissociation. Meanwhile, the separated electron transfers efficiently under the robust built-in electric field induced by the cyano-group and Na, and eventually accumulates in the heptazine ring of CN for the following O2 reduction due to the reinforced electron sink effect caused by Na. As a result, CN-Cy-Na exhibits 4.42 mmol L-1 h-1 productivity with 97.6% selectivity for free radicals and achieves 82.1% total organic carbon removal efficiency in the tetracycline photodegradation within 6 h. Additionally, CN-Cy-Na also shows outstanding photodegradation efficiency of refractory pollutants, including antibiotics, pesticide plastic additives, and dyes. This work presents an innovative approach to manipulating the exciton effect and enhancing charge-carrier mobility within two-dimensional photocatalysts, opening an avenue for precise control of free radical generation.

Boosting excitons dissociation in defective-rich graphitic carbon nitride for efficient hydrogen peroxide photosynthesis and on-site environmental governance

Solar-driven hydrogen peroxide (H2O2) production offers a sustainable strategy to address the ever-growing demand of eco-friendly oxidant and clean fuel, while its efficiency highly relies on the generation of desired reactive oxygen species (ROSs). Herein, we demonstrate that introducing boron-nitrogen vacancy (B-NV) associates in g-C3N4 enables to weaken the robust excitonic effect and promote bound excitons spontaneously dissociating into free charge carriers under ambient conditions. Specifically, the doped B atoms introduced a donor state below the conduction band of g-C3N4, which disturbs charge distribution around heptazine rings and further destabilizes excitons. The concomitant NV, serving as an accepter state locating above the valence band, cooperates with the doped B atoms to form B-NV associates that simultaneously downshifts the conduction band and valence band of g-C3N4. Distinct from the counterpart preferring to activate O2 into 1O2 via an energy-transfer-involved pathway, g-C3N4 featuring with B-NV associates displayed a superior photoactivity of visible-light-driven two-electron oxygen reduction reaction for H2O2 production with a yield of 182 μmol h−1 and selectivity of 100%. The produced H2O2 could effectively degrade organic contaminants and kill typical bacteria. This study highlights the importance of ROSs generation in two-dimensional photocatalysts for sustainable solar-to-chemical conversion and on site environmential governance.

Ultrathin two-dimensional photocatalysts for carbon dioxide reduction into fuels and chemicals

The extensive burning of fossil fuels has caused energy shortages and worsened the greenhouse effect, posing a significant threat to human survival and development. The use of solar energy as a renewable source to reduce CO2 emissions and produce green fuels and high-value chemicals is seen as a promising solution to the ongoing energy crisis. Ultrathin two-dimensional photocatalysts have large surface areas and numerous low-coordination surface atoms, giving them substantial potential for highly efficient photocatalytic performance. These materials can reduce carrier transmission distance, enhance reactant adsorption and activation (e.g., CO2 and H2O), lower energy barriers, facilitate specific reactions, inhibit competing reactions, and regulate catalytic efficiency and selectivity. This article provides a concise overview of ultrathin two-dimensional semiconductor synthesis, clarifies catalytic mechanisms, explores various photocatalytic applications, and outlines strategies to enhance photoconversion performance. It also emphasizes the primary challenges and opportunities faced by ultrathin photocatalysts. We anticipate that this review will offer valuable insights for further research in two-dimensional photocatalysis and encourage the practical application of these unique materials in energy conversion.

Effect of ethylene glycol chelated on ultrathin TiO2(B) nanosheets on the photocatalytic selective benzyl alcohol oxidation

The two-dimensional (2D) photocatalysts have been paid intensive attention in catalysis due to their excellent activity, which was greatly improved by the higher exposure of active sites and a facile reaction platform, and the separation efficiency of charge carriers. Herein, TiO2(B) nanosheets, which were synthesized via solvothermal method in ethylene glycol, could photocatalytically oxidize benzyl alcohol to benzaldehyde with high selectivity. The study revealed that the material's photocatalytic performance is highly influenced by the surface-chelated ethylene glycol. The pristine TiO2(B) was effective in selectively photocatalytic oxidizing benzyl alcohol, achieving a 94.5 % conversion, while the conversion decreased to 55 % after the elimination of the surface ethylene glycol. The presence of ethylene glycol on the surface of TiO2(B) nanosheets benefits the transfer of photogenerated charge carriers and improves charge separation efficiency. It is favorable for the selective formation of singlet oxygen (1O2) species, which results in enhanced photocatalytic activity and selectivity. We believe that our findings can shed light on the importance of the surface species and properties of photocatalysts in photocatalysis, and pave an avenue for the design and preparation of high-efficiency photocatalysts with unique surface properties.

Computational prediction of two-dimensional o-Al2N2 under applied strain for boosting the photocatalytic hydrogen evolution reaction performance

Photocatalytic water splitting for clean hydrogen fuel production provides a promising approach to solve the energy and environmental issues. Recently, two-dimensional (2D) photocatalysts have attracted growing interest owing to their short carrier diffusion path, abundant active sites and large surface area. This study explores the photocatalytic performance of 2D orthorhombic dialuminum dinitride (o-Al2N2) using density functional theory. The computational results show that the o-Al2N2 monolayer has a semiconductor character with indirect and moderate bandgap. Moreover, this system exhibits high light absorption in the visible region, referring to its high capacity for harvesting sunlight. Meanwhile, under neutral pH, the band edge positions are suitable to straddle water redox potentials and the hydrogen evolution reaction is energetically favorable to allow hydrogen production on the surface of 2D o-Al2N2 compound. More importantly, the photocatalytic activity of o-Al2N2 monolayer is significantly improved under slight biaxial compressive strain. Therefore, our findings suggest that the o-Al2N2 nanomaterial is a highly efficient 2D photocatalyst for hydrogen production via water splitting under neutral pH.

An Ab Initio Study of Two Dimensional SnX2 and Janus SnXY (X = S, Se) Nanosheets as Potential Photocatalysts for Water Splitting

Discriminating appropriate two-dimensional (2D) photocatalysts for hydrogen generation is among the most prospective schemes to tackle with environmental contaminations. Unfortunately, the inferior capability to harvest solar light together with fast recombination of photoexcited carriers can severely reduce the catalytic ability with consequent limited commercial applications. In this work, a series of single-layer MXY (M = Ge, Sn; X, Y = S, Se, and Te) containing T- and H-phases about photocatalytic capabilities are systematically explored by first-principles calculations. First, the T- and H-MXY monolayers possess transformable band gaps of 0–2.37 and 0–1.49 eV, respectively. Astonishingly, the values of T-GeS2, T-SnS2, T-SnSe2, T-SnSSe, and H-SnS2 monolayers are higher than the threshold of redox potential difference (1.23 eV). Also, importantly, the carrier mobilities of anisotropic T-MXY monolayers can reach ∼1 × 104 cm2 V–1 s–1, which can rapidly transfer and accelerate the separation of the photoexcited carriers during photocatalytic reactions. Inspired by these significant benefits, the T-MXY monolayers have been built for photocatalytic water-splitting. Significantly, the driving force of photoexcited carriers in T-SnX2 and Janus T-SnSSe monolayers can greatly promote during the redox reactions. Furthermore, the hydrogen reduction and water oxidation reactions of T-SnX2 and T-SnXY monolayers can proceed spontaneously under irradiation. In addition, the few-layer and even monolayer T-SnS2 and T-SnSe2 have been experimentally synthesized in the literature. The potential photocatalysts of single-layer T-MXY have the 0.25–0.29 J m–2 cleavage energies, and ab initio molecular dynamics simulations further validate their stability. Our results provide support for 2D group-IV–VI chalcogenides for photocatalytic water splitting.

Two-dimensional [formula omitted] (X = Si, Ge; Y = S, Se, Te) family with potential application in photocatalysis

Photocatalysis is an attractive route for energy harvesting and pollution mitigation, however, designing an optimal catalyst is rather challenging. Motivated by fundamental interest and potential applications, the investigations of two-dimensional (2D) photocatalyst are important subjects in solar energy conversion. In this work, the stability, electronic, and optical properties of 2D Cr2X2Y6 (X = Si, Ge; Y = S, Se, Te) family are investigated to explore their photocatalytic activity for water splitting. Density functional theory (DFT) and ab-initio molecular dynamics (AIMD) calculations were employed. The electronic band structure calculations indicate that all these monolayers, except Cr2Ge2Te6 and Cr2Si2Te6, have an adequate bandgap, as well as suitable band-edge positions for photocatalytic water splitting reactions, specifically under acidic conditions. Moreover, the studied materials show strong capability of harvesting sunlight, that is essential for photocatalytic activity. Remarkably, Cr2Ge2Se6 and Cr2Si2Se6 monolayers exhibited high solar-to-hydrogen energy conversion efficiencies of 14.89% and 13.26%, respectively. The presented results pave the way for designing other electronically optimized layered photocatalysts for water splitting.

The enhanced visible light driven photocatalytic activity of zinc porphyrin/g-C3N4 nanosheet for efficient bacterial infected wound healing

Graphitic carbon nitride (g-C3N4) has received much attention as a metal-free polymeric two-dimensional photocatalyst for antibiotic-free antibacterial application. However, the weak photocatalytic antibacterial activity of pure g-C3N4 stimulated by visible light limits its applications. Herein, g-C3N4 is modified with Zinc (II) meso-tetrakis (4-carboxyphenyl) porphyrin (ZnTCPP) by amidation reaction to enhance the utilization of visible light and reduce the recombination of electron-hole pairs. The composite (ZP/CN) is used to treat bacterial infection under visible light irradiation with a high efficacy of 99.99% within 10 min due to the enhanced photocatalytic activity. Ultraviolet photoelectron spectroscopy and density flooding theory calculations indicate the excellent electrical conductivity between the interface of ZnTCPP and g-C3N4. The formed built-in electric field is responsible for the high visible photocatalytic performance of ZP/CN. In vitro and in vivo tests have demonstrated that ZP/CN not only possesses excellent antibacterial activity upon visible light irradiation, but also facilitates the angiogenesis. In addition, ZP/CN also suppresses the inflammatory response. Therefore, this inorganic–organic material can serve as a promising platform for effective healing of bacteria-infected wounds.

Surface Boronizing Can Weaken the Excitonic Effects of BiOBr Nanosheets for Efficient O2 Activation and Selective NO Oxidation under Visible Light Irradiation.

The photocatalytic O2 activation for pollutant removal highly depends on the controlled generation of desired reactive oxygen species (ROS). Herein, we demonstrate that the robust excitonic effect of BiOBr nanosheets, which is prototypical for singlet oxygen (1O2) production to partially oxidize NO into a more toxic intermediate NO2, can be weakened by surface boronizing via inducing a staggered band alignment from the surface to the bulk and simultaneously generating more surface oxygen vacancy (VO). The staggered band alignment destabilizes excitons and facilitates their dissociation into charge carriers, while surface VO traps electrons and efficiently activates O2 into a superoxide radical (•O2-) via a one-electron-transfer pathway. Different from 1O2, •O2- enables the complete oxidation of NO into nitrate with high selectivity that is more desirable for safe indoor NO remediation under visible light irradiation. This study provides a facile excitonic effect manipulating method for layered two-dimensional photocatalysts and sheds light on the importance of managing ROS production for efficient pollutant removal.

Two-dimensional photocatalyst with highly efficient and stable visible light photocatalytic activity

Hex ammonium molybdate (AHM), ammonium nitrate (NH4NO3), and glycine were used as the precursors in a microwave-assisted solution combustion synthesis (WSCS) process to create foam-like MoO2 nanoparticles. Methodically investigated was the effect of the glycine/NH4NO3 ratio (=0.25, 0.50, 0.75, 1.0 and 1.25) on the finished goods. The findings indicate that the final morphologies and phases of the products are virtually influenced by the value of Φ. MoO2 nanoparticles measuring 20 to 30 nm can be successfully composited under the condition of Φ=0.50 to produce a foam-like result. The photocatalytic activity of foam-like MoO2 nanoparticles was tested with several pollutants. The results show that foam-like MoO2 nanoparticles have good degradability and stability. The photocatalytic mechanism and fabrication mechanism of foam-like MoO2 has been presented in detail. Using foam-like MoO2-based photocatalyst materials for energy transfer and environment protection is supported by this research.

Two-dimensional photocatalyst with highly efficient and stable visible light photocatalytic activity

Hex ammonium molybdate (AHM), ammonium nitrate (NH4NO3), and glycine were used as the precursors in a microwave-assisted solution combustion synthesis (WSCS) process to create foam-like MoO2 nanoparticles. Methodically investigated was the effect of the glycine/NH4NO3 ratio (=0.25, 0.50, 0.75, 1.0 and 1.25) on the finished goods. The findings indicate that the final morphologies and phases of the products are virtually influenced by the value of Φ. MoO2 nanoparticles measuring 20 to 30 nm can be successfully composited under the condition of Φ=0.50 to produce a foam-like result. The photocatalytic activity of foam-like MoO2 nanoparticles was tested with several pollutants. The results show that foam-like MoO2 nanoparticles have good degradability and stability. The photocatalytic mechanism and fabrication mechanism of foam-like MoO2 has been presented in detail. Using foam-like MoO2-based photocatalyst materials for energy transfer and environment protection is supported by this research.

Novel 2D photocatalyst of copper-doped carbon quantum dot CD(Cu) loaded with ultrathin Ni-MOL for degradation of tetracycline.

Broadening the light absorption range and suppressing the carrier complexation are the two keys to enhance the photocatalytic activity. In this work, a novel two-dimensional (2D) photocatalyst was successfully prepared by modified hydrothermal method and applied in tetracycline (TC) degradation. The degradation rate of CD(Cu)-Ni-MOL for TC reached 93.5% within 60 min under the visible light condition. The improved photocatalytic performance of CD(Cu)-Ni-MOL was attributed to the constructed 2D layered structure and the special properties of CD(Cu). The doped Cu in carbon dots (CDs) exhibited excellent photocatalytic performance among the elements of Cu, Zn, Ni, Co and Fe. The order of photocatalytic performance improvement was Cu > Zn > Ni > Co > Fe. In addition, a possible degradation pathway for TC was proposed. This work confirms the great potential of CD(Cu)-Ni-MOL as a highly efficient photocatalyst in removing tetracycline pollutants in water.

First-principles study of the effect of point defects (Hi-VAl) on the magnetic and photocatalytic properties of monolayer AlN: Be/Mg/Ca

Single-layer AlN is obtained by chemical vapor deposition and molecular beam epitaxy; therefore, Hi impurities will inevitably remain in AlN in a vacuum environment. Hi impurities are often overlooked and VAl is experimentally challenging. Given these problems, the effects of point defects (Hi-VAl) on the photocatalytic and magnetic properties of monolayer AlN: Be/Mg/Ca were studied using first-principles calculations. Results showed that monolayer Al34HiBeN36 had relatively high stability, relatively strong carrier activity, relatively strong visible light effect, long life, relatively difficult carrier recombination, and relatively good oxidation–reduction properties. The results provide a theoretical reference for designing novel two-dimensional photocatalysts.

Electron cloud density localized graphitic carbon nitride with enhanced optical absorption and carrier separation towards photocatalytic hydrogen evolution

High photogenerated carrier recombination and poor visible light response in symmetry graphitic carbon nitride are two classical problems for photocatalytic hydrogen evolution. In this work, we rationally design a novel carbon nitride (DPCN) with asymmetric embeddedness of pyridine ring. The embedded pyridine ring modulates the localization of electron cloud density, resulting in a narrowed bandgap and an enhanced carriers’ separation efficiency. They are further confirmed by UV–vis spectra and femtosecond transient absorption (fs-TA) spectroscopy, whose results are consistent with DFT theoretical calculations. This DPCN catalyst shows enhanced photocatalytic hydrogen evolution rate of 180.5 μmol h−1 and the apparent quantum efficiency of 14.6 % at 420 nm, surpassing most reported g-C3N4-based photocatalysts. This work provides a new sight on designing two-dimensional photocatalysts by modulating the localization of electron cloud density through breaking topological symmetry.