Metal-free Photocatalyst Research Articles

A facile approach for fabricating g-C3N4-based materials as metal-free photocatalysts

This study presents a novel, straightforward approach for synthesizing graphitic carbon nitrides (g-C3N4, g-CN) from melamine, requiring merely 30 minutes of thermal holding at temperatures ranging from 400 to 550 °C in an atmosphere comprising either nitrogen or air. Elemental analysis, X-ray powder diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), diffuse reflectance (UV-Vis DRS), photoluminescence (PL) spectroscopy and scanning electron microscopy (SEM) were employed to assess the quality of the as-prepared powders. Furthermore, theoretical calculations utilizing the Density Functional Theory (DFT) method were conducted to reinforce the experimental findings of the research. A further investigation of the thermal stability of the selected sample was conducted using a unique combination of thermogravimetry–coupled with differential scanning calorimetry, quadrupole mass spectrometry (TG-DSC-MS) and advanced temperature-programmed desorption (TPD) analyzes. The current study focuses on the effect of synthesis conditions (temperature and nitrogen/air environment) on the structure, morphology, and photocatalytic performance of g-C3N4 compounds synthesized using this approach. The g-C3N4-based materials were examined as potential photocatalysts using the acid orange 7 (AO7) photodegradation methodology. To enable comparison of the photodegradation experiments, two separate lamps with wavelengths of 360 nm (UV light) and 420 nm (VIS light) were utilized. The primary objective was to present a novel method for the synthesis of g-C3N4-based materials. This was achieved by demonstrating that organic composites generated at lower temperatures have the best photocatalytic capabilities. Furthermore, the approach to achieving high-quality photocatalysts was shown to be cost-effective, environmentally friendly, and scalable.

Visible light-induced synthesis of benzothiazole derivatives using graphitic carbon nitride as a recyclable metal-free photocatalyst

Visible light-induced synthesis of benzothiazole derivatives using graphitic carbon nitride as a recyclable metal-free photocatalyst

Sustainable Photocatalytic Mitigation of 2-Mercaptobenzothiazole by Expired Medicine Derived Metal-Free Graphitic Carbon Nitride Photocatalyst

Sustainable Photocatalytic Mitigation of 2-Mercaptobenzothiazole by Expired Medicine Derived Metal-Free Graphitic Carbon Nitride Photocatalyst

Energy-transfer-enabled photocatalytic transformations of aryl thianthrenium salts

Aryl thianthrenium salts are valuable in photocatalysis but traditionally require external electron donors for activation. This study introduces an energy transfer (EnT) strategy for the activation of aryl thianthrenium salts using 2,3,4,5,6-penta(carbazol-9-yl)benzonitrile (5CzBN) as a metal-free photocatalyst, eliminating the need for external donors. Utilizing this EnT approach, we achieve C–H deuteration of arenes under visible light with CDCl3 as a deuterium source to synthesize various deuterated aromatic compounds, including important natural products and pharmaceuticals. Additionally, this strategy enables diverse functionalizations including borylation, arylation, cyanation, and selenylation, enhancing the applicability of aryl sulfonium salts in environmentally friendly photocatalysis.

Oxygen-Doped Porous Ultrathin Graphitic Carbon Nitride Nanosheets for Photocatalytic Hydrogen Evolution and Rhodamine B Degradation.

Graphite phase carbon nitride (g-C3N4) is a highly promising metal-free photocatalyst, but its low activity, due to limited quantum efficiency and small specific surface area, restricts its practical application. While exfoliating bulk crystals into porous thin-layer nanosheets and incorporating dopants have been shown to improve photocatalytic efficiency, these methods are typically complex, time-consuming, and costly processes. In this study, we developed a simple approach to synthesize oxygen-doped porous g-C3N4 (OCN) nanosheets. The resulting OCN exhibited significantly enhanced light absorption and visible-light photocatalytic activity compared to bulk g-C3N4 (BCN) and g-C3N4 (CN). The OCN achieved an impressive hydrogen evolution reaction (HER) rate of 8.02 mmol g-1 h-1, eight times greater than BCN, and demonstrated a high Rhodamine B (RhB) degradation rate of 97.3 % owing to the generation of abundant singlet oxygen. These improvements in photocatalytic performance are attributed to the narrow band gap and enhanced electron transfer properties, suggesting a promising route for the efficient design of g-C3N4-based photocatalysts.

Facile synthesis of CQD/g-C3N4 as a highly effective metal-free photocatalyst for the degradation of carmoisine and indigo carmine dye

The development of extensive dye pollution in the water ecosystem seriously endangers the health of the living organism. For effectively eradicating dyecontaminants from water bodies, photocatalysis is consideredan effective, energy-consumption, inexpensive disinfection technique. As an alternative to conventional metal-based catalysts, heterogeneous metal-free photocatalysts are more sustainable and kinder to the environment. Here, we reported the simplehydrothermalchemical production of Carbon Quantum dots (CQD)-doped graphitic carbon nitride(GCN). Analytical instruments such as XRD, SEM, FE-SEM, HR-TEM, EDX, FT-IR, thesurface area of BET analysis, photoluminescence, and UV–vis spectroscopy, zeta potentialwere used to characterize the as-prepared CQD doped GCN (CDCN). The degradation studies reveal that the CDCN catalyst displays the highest rate of degradation performance than pure GCN. Within 60 min, it shows 96 % degradation toward indigo Carmine (IC) and 93 % decomposition towards carmoisine dye (CM). Significant e−/h+ separation, an increased surface area, and a high redox potential capacity to induce charge bears may all contribute to the CDCN catalyst’s enhanced photocatalytic degradation efficiency. The efficiency of the photocatalytic process was optimized by studying and altering many variables. These include Dye concentration, catalyst concentration, and variation of the pH solution were some of these. The nanocomposite exhibited excellent stability after three successive runs of the photocatalytic procedure. According to the kinetics analysis results indicate that the photocatalytic decomposition of Indigo Carmine (IC) and carmoisine (CM) dye follows pseudo-first-order kinetics. For better photodegradation performance, a potential photocatalytic method employing several pairs of electron-hole acceptor scavengershas been put forth. Based on the positionsof the band gap and the result of the characterization, a feasible mechanismpathway for charge carriers was also presented.

Photocarrier Dynamics of Two-Dimensional Aza-Fused Covalent Organic Frameworks as Bifunctional Photocatalysts toward Overall Water Splitting.

Designing high-efficiency bifunctional photocatalysts toward photoinduced overall water splitting is one of the most promising and challenging research directions for clean energy generation. By employing static electronic structure calculation and nonadiabatic molecular dynamics (NAMD) simulation, we herein established a recently synthesized two-dimensional (2D) aza-fused covalent organic framework (aza-COF) as a potential bifunctional photocatalyst toward overall water splitting reactions. Our calculated results reveal that the overpotentials for hydrogen evolution reaction and oxygen evolution reaction are only 0.06 and 0.31 V, respectively, at pH = 4. The dynamics of photoexcited charge carriers studied through NAMD simulation predicts the electron-hole recombination time (25.15 ns), and this confirms that the photogenerated electron and hole carriers migrate to the active sites for the occurrence of reaction before they recombine. Therefore, our results suggest that the 2D aza-COFs exhibit great potential as metal-free and single-material photocatalysts toward overall water splitting under visible light.

ZnIn2S4 nanosheets with geometric defects for enhanced solar-driven hydrogen evolution and wastewater treatment

The key to development of high-performance and low cost photocatalysts hydrogen evolution and waste degradation is to realize efficient photo-generated charge carrier separation and surface catalytic reaction simultaneously without noble metal co-catalyst. To achieve this goal, a noble metal free ZnIn2S4 photocatalyst with geometric defects has been constructed, in which [In-S]4 tetrahedral vacancies (named as (InS)v) on the surface are created by removing the In and S atoms. Further mechanistic investigation has revealed that the (InS)v not only works as the active sites for reductive reaction, but also improves photo-generated electron-hole separation. As a result, the solar-driven hydrogen evolution rate reaches 10.70 mmol/gh without co-catalyst after optimizing the densities of the (InS)v. The apparent quantum efficiency at 380 nm, 395 nm, 420 nm, 450 nm and 520 nm is as high as 14.0 %, 17.1 %, 12.1 %, 8.2 % and 2.4 %, respectively. In addition, these photocatalysts also achieve a rate of 97.78 % and 91.27 % of RhB and MO within 3 and 60 min, respectively. This work show-case a novel approach to develop dual functional and noble metal free photocatalysts for efficiently utilizing solar energy for hydrogen generation and wastewater treatment.

Structurally Locked High-Crystalline Covalent Triazine Frameworks Enable Remarkable Overall Photosynthesis of Hydrogen Peroxide.

The development of green and efficient hydrogen peroxide (H2O2) production is of great interest but remains challenging. Herein, we develop a new and simple strategy via locking the coplanarity in highly crystalline covalent triazine frameworks (CTFs) to remarkably boost direct photosynthesis of H2O2 from oxygen and water. The exfoliated ultrathin 2D-CTF nanosheets exhibit excellent photocatalytic H2O2 evolution with an ultrahigh solar-to-chemical efficiency of 0.91% and a superb apparent quantum yield of 16.8% at 420 nm, surpassing all previous CTFs and most of the metal-free photocatalysts ever reported. Our detailed experimental and theoretical studies reveal that the spatially locked structure in the crystalline CTF photocatalyst can not only greatly enhance the separation and transfer of photoexcited charge-carriers for promoting H2O2 photogeneration but also alter the local electronic structures that unexpectedly turn water oxidation from a four-electron route to a two-electron pathway, resulting in a 100% atom utilization efficiency. This work provides valuable insights into the designed synthesis of highly efficient metal-free photocatalysts and precise control over photocatalytic reaction pathways in organic materials.

Azobenzene-Bridged Covalent Organic Frameworks Boosting Photocatalytic Hydrogen Peroxide Production from Alkaline Water: One Atom Makes a Significant Improvement.

Covalent organic frameworks (COFs) have been demonstrated as promising photocatalysts for hydrogen peroxide (H2O2) production. However, the construction of COFs with new active sites, high photoactivity, and wide-range light absorption for efficient H2O2 production remains challenging. Herein, we present the synthesis of a novel azobenzene-bridged 2D COF (COF-TPT-Azo) with excellent performance on photocatalytic H2O2 production under alkaline conditions. Notably, although COF-TPT-Azo differs by only one atom (-N=N- vs. -C=N-) from its corresponding imine-linked counterpart (COF-TPT-TPA), COF-TPT-Azo exhibits a significantly narrower band gap, enhanced charge transport, and prompted photoactivity. Remarkably, when employed as a metal-free photocatalyst, COF-TPT-Azo achieves a high photocatalytic H2O2 production rate up to 1498 μmol g-1 h-1 at pH = 11, which is 7.9 times higher than that of COF-TPT-TPA. Further density functional theory (DFT) calculations reveal that the -N=N- linkages are the active sites for photocatalysis. This work provides new prospects for developing high-performance COF-based photocatalysts.

Boosting lactic acid photocatalytic synthesis from biomass sugars: The synergistic effect of N-doped carbon dots on ultrathin carbon nitride

The green and sustainable production of lactic acid via photocatalytic conversion of biomass-derived sugars is highly significant owing to its enhanced efficiency and reduced energy requirements. Consequently, the investigation has engineered a metal-free photocatalyst (NCDs/CCN), consisting of N-doped carbon dots (NCDs) and ultrathin carbon nitride (CCN). This catalyst has an enhanced light absorption range, facilitating a marked acceleration in the separation rate of photogenerated carriers. It has demonstrated the capability to achieve a lactic acid yield of up to 87.6 % in just 90 min with a mere 20 mg catalyst concentration in a xylose-alkali system. Electron Paramagnetic Resonance (EPR) and quenching experiments indicate that superoxide radicals (·O2−) are the primary oxidizing active species in the photocatalytic system, followed by h+, ·OH, and 1O2. DFT analysis suggests nitrogen doping enhances interaction with xylose, lowering adsorption energy and accelerating lactic acid generation, thus improving economic feasibility and sustainability.

Facilitating exciton dissociation in conjugated microporous polymers for photocatalytic degradation of tetracycline via a gradient N doping strategy

As a leading green wastewater treatment technology, organic semiconductor photocatalysis for tetracycline (TC) degradation is widely recognized but currently constrained by excessive exciton binding energies and rapid charge recombination. In this work, conjugated microporous polymers (CMPs) with five-membered heterocyclic ring have been fabricated by gradient doping of nitrogen at the monomer level. It demonstrates satisfactory photocatalytic performance, with thiadiazole introduced into the unit, achieving a TC removal rate of 95.6% within 30 min under visible light. The underlying origin of the preferable property lies in the lower exciton binding energy (Eb) with the assistance of the donor–acceptor (D-A) structure constructed by thiadiazole monomer and triazine skeleton. Density Functional Theory (DFT) calculations reveal that this five-membered heterocyclic structure can appropriately regulate the local charge distribution and increase the dipole moment, thus accelerating the migration dynamics of charge carriers in the degradation process. This study provides a novel insight into the modulation of polymer exciton Eb and enlightens the designation of metal-free photocatalysts based on antibiotic degradation.

(Ag–NiO)/g-C3N4 with enhanced photocatalytic activity for hydrogen evolution under simulated sunlight

g-C3N4 is a promising metal-free photocatalyst for hydrogen production, whose application is difficult due to the low mobility of charge carriers and rapid electron-hole recombination. Here we propose a new route to improve its response to simulated sunlight and prevent electron-hole recombination by grafting mixed Ag–NiO (1:1 nominal Ag/NiO weight ratio) materials, as an alternative to platinum group metal co-catalysts. g-C3N4 was prepared by urea pyrolysis, whereas Ag–NiO was prepared by a co-precipitation method, and then the composites were prepared by physical mixing using sonication-grinding. The presence of Ag–NiO on the surface plays a key role in accepting excited electrons and enhancing their lifetime for a subsequent reduction of protons to hydrogen. Hydrogen production was carried out from the photoreforming of ethanol under simulated sunlight. The results revealed that 2% (Ag–NiO)/g-C3N4 is effective among others with 5.2 times higher H2 production than unmodified g-C3N4. The percentage of ethanol in the ethanol/water ratio is very important as we have found that with increasing its quantity, the evolution of hydrogen becomes significant.

In-Situ Anchoring of Co Single-Atom Synergistically with Cd Vacancy of Cadmium Sulfide for Boosting Asymmetric Charge Distribution and Photocatalytic Hydrogen Evolution.

In the context of reshaping the energy pattern, designing and synthesizing high-performance noble metal-free photocatalysts with ultra-high atomic utilization for hydrogen evolution reaction (HER) still remains achallenge. In a streamlined synthesis process, in-situ single atom anchoring is performed in parallel with HER by irradiating a precursory defect-state CdS/Co suspension (Co-DCdS-Ss) system under simulated sunlight and the in-situ synthesizing single-atom Co photocatalyst (Co5:DCdS) exhibits further improved catalytic performance (60.10 mmolg-1h-1) compared with Co-DCdS-Ss (18.09 mmolg-1h-1), reaching an apparent quantum yield of 57.6% at 500nm and a solar-chemical energy conversion efficiency (SCC) of 6.26% at AM 1.5G. In-depth characterization tests and density functional theory (DFT) calculations prove that the anchoring of Co single atom deepens the asymmetric charge distribution of the two-coordination S atom adjacent to the cadmium vacancy (VCd). The synergy between electron delocalization VCd and Co single atom on the catalyst surface is constructed, which bifunctional sites responsible for boosting water adsorption-dissociation and hydrogen evolution. This study advances the understanding of the underlying mechanisms of synergy between surface defects and metal single atoms and opens a new horizon for the development of advanced materials in the field of photocatalysis.

N vacancies and OH/C=O co-modified g-C3N4 photoactivated peroxymonosulfate for the degradation of tetracycline: Synergistic promotion effect between excitons and carriers

Activation of peroxymonosulfate (PMS) to generate reactive oxygen species (ROS) for pollutant degradation via metal-free photocatalysts is an important green wastewater treatment and remediation method, but the pathway for generating ROS via exciton effects in catalysts is often overlooked. In this study, OH/C=O co-modified N-defective rod-shaped carbon nitride (Nv-CN-O) was designed and synthesized by soft template and alkali hydrothermal method. In the Nv-CN-O/PMS/Light system, there was a synergistic degradation of tetracycline (TC) by carriers and excitons, with a degradation rate 2.15 times higher than that of CN/PMS/Light. N vacancies and OH/C=O enhanced the adsorption to PMS, accelerated the charge transfer process, and activated PMS to generate ·O2− dominated reactive species. The functional group OH/C=O promoted the production of triplet excitons that through the energy transfer pathway to promote the production of 1O2. Abundant ROS were involved in the TC degradation process, and three possible TC degradation pathways were proposed. Nv-CN-O has strong anti-interference ability in actual water bodies, shows a promoting effect on the degradation of TC, which has practical application potential.

Exploring the formation of S-scheme heterojunctions in CuFe2O4/Bi2MoO6 porous cubes for photocatalytic removal of tetracycline

Exploring highly active and noble metal-free photocatalysts for the efficient photocatalytic degradation of antibiotics is of great significance. The CuFe2O4 nanostructured cube is synthesized by using a self-sacrificial template strategy, and two-dimensional Bi2MoO6 nanosheets are grown on the surface of CuFe2O4 through a solvothermal method to construct CuFe2O4/Bi2MoO6 S-scheme heterostructure. The CuFe2O4/Bi2MoO6 composite material exhibits eminent photocatalytic activity for the degradation of TC under simulated sunlight, with the optimal ratio CFO/BMO-2 achieving a degradation rate of 98.54 % within 30 min (initial concentration of TC: 50 mg L−1). In addition, CFO/BMO-2 also has excellent magnetic recyclability and cycling ability. Rice cultivation tests demonstrate that the biotoxicity of TC is effectively removed. Density functional theory calculations and in-situ irradiated X-ray spectroscopy deeply reveal the mechanisms of charge separation and transfer of S-scheme heterojunctions in CuFe2O4/Bi2MoO6. The construction of S-scheme heterojunctions promotes the separation of photo-induced charge carriers and improves photocatalytic degradation performance by retaining holes and electrons with strong redox ability. The work provides a practicable method for constructing efficient spinel photocatalysts to drive wastewater treatment reactions, and the constructed magnetically recyclable photocatalysts have certain practical application potential.

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.

A metal-free cascaded process for efficient H2O2 photoproduction using conjugated carbonyl sites

Carbon-based metal-free catalysts are promising green catalysts for photocatalysis and electrocatalysis due to their low cost and environmental friendliness. A key challenge in utilizing these catalysts is identifying their active sites, given their poor crystallinity and complex structures. Here we demonstrate the key structure of the double-bonded conjugated carbon group as a metal-free active site, enabling efficient O2 photoreduction to H2O2 through a cascaded water oxidation − O2 reduction process. Using ethylenediaminetetraacetic acid as a precursor, we synthesized various carbon-based photocatalysts and analyzed their structural evolution. Under the polymerization conditions of 260 °C to 400 °C, an N-ethyl-2-piperazinone-like structure was formed on the surface of the catalyst, resulting in high photocatalytic H2O2 photoproduction (2884.7 μmol g−1h−1) under visible light. A series of control experiments and theoretical calculations further confirm that the double-bond conjugated carbonyl structure is the key and universal feature of the active site of metal-free photocatalysts.

Benzothiadiazole-Based Ordered Mesoporous Polymer as a Versatile, Metal-Free Heterogeneous Photocatalyst.

Visible-light active heterogeneous organophotocatalysts have recently gained considerable interest in organic synthetic community. Ordered mesoporous polymers (OMPs) are highly promising as heterogeneous alternative to traditional precious metal/organic dyes-based photocatalysts. Herein, we report the preparation of a benzothiadiazole functionalized OMPs (BT-MPs) through a "bottom-up" strategy. High ordered periodic porosity, large surface area, excellent stability and rational energy-band structures guarantee the high catalytic activity of BT-MPs. As a result, at least six conversions, e. g., the [3+2] cycloaddition of phenols with olefins, the selective oxidation of sulfides, the C-3 thiocyanation of indole and the aminothiocyanation of β-keto ester, could be promoted smoothly by BT-MPs. In addition, BT-MPs was readily recovered with well maintaining its photocatalytic activity and could be reused for at least eight times. This study highlights the potential of exploiting photoactive OMPs as recyclable, robust and metal-free heterogeneous photocatalysts.

Enhancing Fenton-like reaction mediating performance of covalent organic frameworks through porosity modification

Covalent organic framework (COF) catalytic photocatalysts mediating Fenton-like reactions have been applied to the treatment of organic dyes in printing and dyeing wastewater. However, the photocatalytic performance of original COF is often unsatisfactory. This study investigated the impact of porosity modification strategies on the performance of COF photocatalysts in mediating the removal of organic dyes via Fenton-like reaction. Porosity modification was achieved by increasing the concentration of acetic acid (HAc) catalyst during COF preparation. The modified TAPB-DMTA COF (12M COF) exhibited excellent adsorption and photocatalytic properties. The Fenton-like reaction mediated by 12M COF photocatalysis removed nearly 96% of malachite green (MG) within 20 min, with a rate constant of 0.091 min−1, which was 2.9 and 6.5 times higher than that of g-C3N4 and original COF under the same reaction conditions, respectively. Additionally, the modulation mechanism of porosity modification on COF photocatalysis was explored. The conduction band (CB) of COF was reduced from −0.14 eV to −0.38 eV after porosity modification, facilitating the generation of longer-lived O2•- in the reaction system, which was conducive to efficient MG removal. Anti-interference experiments showed that the photocatalytic Fenton-like reaction system based on 12 M COF was less affected by common anions, cations and dissolved organics, while maintaining a high MG removal rate in tap water, mid-water, secondary clarifier effluent and river water. In summary, porosity modification was an effective strategy to improve the catalytic performance of original COFs. This study presented an efficient metal-free photocatalyst modification strategy for the Fenton-like reaction while avoiding the production of toxic by-products during dye degradation.