Ultrafast plasma method allows rapid immobilization of monatomic copper on carboxyl-deficient g-C3N4 for efficient photocatalytic hydrogen production.

Transition-metal monometallic photocatalysts have received extensive attention owing to the maximization of atomic utilization efficiency. However, in previous related works, single-atom loading and stability are generally low due to limited anchor sites and mechanisms. Recently, adding transition-metal monatomic sites to defective carbon nitrides has a good prospect, but there is still lack of diversity in defect structures and preparation techniques. Here, a strategy for preparing defect-type carbon-nitride-coupled monatomic copper catalysts by an ultrafast plasma method is reported. In this method, oxalic acid and commercial copper salt are used as a carboxyl defect additive and a copper source, respectively. Carbon nitride samples containing carboxyl defects and monatomic copper can be processed within 10 min by one-step argon plasma treatment. Infrared spectroscopy and nuclear magnetic resonance prove the existence of carboxyl defects. Spherical aberration electron microscopy and synchrotron radiation analysis confirm the existence of monatomic copper. The proportion of monatomic copper is relatively high, and the purity is high and very uniform. The Cu PCN as-prepared shows not only high photo-Fenton pollutant degradation ability but also high photocatalytic hydrogen evolution ability under visible light. In the photocatalytic reaction, the reversible change of Cu+/Cu2+ greatly promotes the separation and transmission of photogenerated carriers and improves the utilization of photoelectrons. The photocatalytic hydrogen evolution rate of the optimized sample is 8.34 mmol g-1·h-1, which is 4.54 times that of the raw carbon nitride photocatalyst. The cyclic photo-Fenton experiment confirms the catalyst has excellent repeatability in a strong oxidation environment. The synergistic mechanism of the photocatalyst obtained by this plasma is the coordination of single-atom copper sites and carboxyl defect sites. The single copper atoms incorporated can act as an electron-rich active center, enhancing the h+ adsorption and reduction capacity of Cu PCN. At the same time, the carboxyl defect sites can form hydrogen bonds to stabilize the production of hydrogen atoms and subsequently convert them to hydrogen because of the unstable hydrogen bond structure. This plasma strategy is green, convenient, environment-friendly, and waste-free. More importantly, it has the potential for large-scale production, which brings a new way for the general preparation of high-quality monatomic catalysts.

H2+CO2 Synergistic Plasma Positioning Carboxyl Defects in g-C3N4 with Engineered Electronic Structure and Active Sites for Efficient Photocatalytic H2 Evolution.

Defective functional-group-endowed polymer semiconductors, which have unique photoelectric properties and rapid carrier separation properties, are an emerging type of high-performance photocatalyst for various energy and environmental applications. However, traditional oxidation etching chemical methods struggle to introduce defects or produce special functional group structures gently and controllably, which limits the implementation and application of the defective functional group modification strategy. Here, with the surface carboxyl modification of graphitic carbon nitride (g-C3N4) photocatalyst as an example, we show for the first time the feasibility and precise modification potential of the non-thermal plasma method. In this method, the microwave plasma technique is employed to generate highly active plasma in a combined H2+CO2 gas environment. The plasma treatment allows for scalable production of high-quality defective carboxyl group-endowed g-C3N4 nanosheets with mesopores. The rapid H2+CO2 plasma immersion treatment can precisely tune the electronic and band structures of g-C3N4 nanosheets within 10 min. This conjoint approach also promotes charge-carrier separation and accelerates the photocatalyst-catalyzed H2 evolution rate from 1.68 mmol h-1g-1 (raw g-C3N4) to 8.53 mmol h-1g-1 (H2+CO2-pCN) under Xenon lamp irradiation. The apparent quantum yield (AQY) of the H2+CO2-pCN with the presence of 5 wt.% Pt cocatalyst is 4.14% at 450 nm. Combined with density functional theory calculations, we illustrate that the synergistic N vacancy generation and carboxyl species grafting modifies raw g-C3N4 materials by introducing ideal defective carboxyl groups into the framework of heptazine ring g-C3N4, leading to significantly optimized electronic structure and active sites for efficient photocatalytic H2 evolution. The 5.08-times enhancement in the photocatalytic H2 evolution over the as-developed catalysts reveal the potential and maneuverability of the non-thermal plasma method in positioning carboxyl defects and mesoporous morphology. This work presents new understanding about the defect engineering mechanism in g-C3N4 semiconductors, and thus paves the way for rational design of effective polymeric photocatalysts through advanced defective functional group engineering techniques evolving CO2 as the industrial carrier gas.

CeO2 Structure Adjustment by H2O via the Microwave-Ultrasonic Method and Its Application in Imine Catalysis.

CeO2 with fusiform structures were prepared by the combined microwave-ultrasonic method, and their morphologies and surface structure were changed by simply adding different amounts of H2O (1-5 ml) to the precursor system. The addition of H2O changed the PVP micelle structure and the surface state, resulting in CeO2 with a different specific surface area (64-111 m2 g-1) and Ce3+ defects (16.5%-28.1%). The sample with 2 ml H2O exhibited a high surface area (111.3 m2∙g-1) and relatively more surface defects (Ce3+%: 28.1%), resulting in excellent catalytic activity (4.34 mmol g-1 h-1).

Polymeric structure optimization of g-C3N4 by using confined argon-assisted highly-ionized ammonia plasma for improved photocatalytic activity.

The optimization of the polymeric structure and the modulation of surface amino groups in graphitic carbon nitride (g-CN) are critical but challenging in improving the photoelectric and photocatalytic performances of this polymer semiconductor. Ammonia plasma treatment may provide a fast and useful approach to optimize g-CN materials yet is seriously restricted by the low ionization ability of ammonia. Herein, a confined fast and environmental-friendly ammonia plasma method based on argon-assisted high ionization of NH3 was developed for efficient modification of raw g-CN. Compared with the weakly-ionized pure ammonia plasma which can only introduce amino group onto the surface g-CN, the argon-assisted highly-ionized ammonia plasma treatment obviously contributes to the comprehensively polymeric structure optimization of g-CN, and thus plays a key role in enhancing its light-harvesting and decelerating the recombination of the photogenerated charge carriers. As a result, the argon-assisted highly-ionized ammonia plasma-treated g-CN-Ar+NH3 outperformed the raw g-CN by a 2.5-fold higher photocatalytic reduction of hexavalent chromium and a remarkable 3.8-fold higher photocatalytic H2 evolution activity (up to 957.8 µmol·h-1·g-1) under visible light irradiation. Our findings suggest the great prospects of this novel highly-ionized ammonia plasma treatment method in the controllable modification of semiconductors and polymers.

Surface Amino Group Regulation and Structural Engineering of Graphitic Carbon Nitride with Enhanced Photocatalytic Activity by Ultrafast Ammonia Plasma Immersion Modification.

Surface amino group regulation and structural engineering of graphitic carbon nitride (g-CN) for better catalytic activity have increasingly become a focus of academia and industry. In this work, the ammonia plasma produced by a microwave surface wave plasma generator was developed as a facile source to achieve fast, controllable surface modification, and structural engineering of g-CN by ultrafast plasma treatment in minutes, thus enhancing photocatalytic performance of g-CN. The morphology, surface hydrophilicity, optical absorption properties, and states of C-N bonds were investigated to determine the effect of plasma immersion modification on the g-CN catalyst. The structure and photoelectric features of the plasma-modified samples were characterized by X-ray diffractometry, Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, and electrochemical impedance spectroscopy. The results indicate that the ammonia plasma-treated g-CN-NH3 exhibits an ultrathin nanosheet structure, enriched amino groups, and an ideal molecular structure, a narrower band gap (2.35 eV), extended light-harvesting edges (560 nm), and enhanced electron transport ability. The remarkably enhanced photocatalytic activity demonstrated in the photoreduction and detoxification of hexavalent chromium (Cr(VI)) can be ascribed to the optimization of the structural and photoelectric properties induced by the unique ammonia plasma treatment. The effective and ultrafast approach developed in this work is promising in the surface amino group regulation and structural engineering of various functional materials.