Search Results (22)

The efficient depolymerization of lignin has become a key challenge in the preparation of high-value-added chemicals. Graphitic carbon nitride (g-C₃N₄)-based photocatalytic system shows potential due to its mild and green characteristics over other depolymerization methods. However, its inherent defects, such as a wide band gap and rapid carrier recombination, severely limit its catalytic performance. In this paper, a g-C₃N₄ modification strategy of K⁺ doping and surface alkalinization is proposed, which is firstly applied to the photocatalytic depolymerization of the lignin β-O-4 model compound (2-phenoxy-1-phenylethanol). K⁺ doping is achieved by introducing KCl in the precursor thermal polymerization stage to weaken the edge structure strength of g-C₃N₄, and post-treatment with KOH solution is combined to optimize the surface basic groups. The structural/compositional evolution of the materials was analyzed by XRD, FTIR, and XPS. The morphology/element distribution was visualized by SEM-EDS, and the optoelectronic properties were evaluated by UV–vis DRS, PL, EIS, and transient photocurrent (TPC). K⁺ doping and surface alkalinization synergistically regulate the layered structure of the material, significantly increase the specific surface area, introduce nitrogen vacancies and hydroxyl functional groups, effectively narrow the band gap (optimized to 2.35 eV), and inhibit the recombination of photogenerated carriers by forming electron capture centers. Photocatalytic experiments show that the alkalinized g-C₃N₄ can completely depolymerize 2-phenoxy-1-phenylethanol with tunable product selectivity. By adjusting reaction time and catalyst dosage, the dominant product can be shifted from benzaldehyde (up to 77.28% selectivity) to benzoic acid, demonstrating precise control over oxidation degree. Mechanistic analysis shows that the surface alkaline sites synergistically optimize the C_β-O bond breakage path by enhancing substrate adsorption and promoting the generation of active oxygen species (·OH, ·O₂⁻). This study provides a new idea for the efficient photocatalytic depolymerization of lignin and lays an experimental foundation for the interface engineering and band regulation strategies of g-C₃N₄-based catalysts. Full article

Considering the poor conductivity of Fe₂O₃ and the weak oxygen evolution reaction associated with it, surface hole accumulation leads to electron hole pair recombination, which inhibits the photoelectrochemical (PEC) performance of the Fe₂O₃ photoanode. Therefore, the key to improving the PEC water oxidation performance of the Fe₂O₃ photoanode is to take measures to improve the conductivity of Fe₂O₃ and accelerate the reaction kinetics of surface oxidation. In this work, the PEC performances of Fe₂O₃ photoanodes are synergistically improved by combining loaded an FeOOH cocatalyst and oxygen vacancy doping. Firstly, amorphous FeOOH layers are successfully prepared on Fe₂O₃ nanostructures through simple photoassisted electrodepositon. Then oxygen vacancies are introduced into FeOOH-Fe₂O₃ through plasma vacuum treatment, which reduces the content of Fe-O (O_L) and Fe-OH (-OH), jointly promoting the generation of oxygen vacancies. Oxygen vacancy can increase the concentration of most carriers in Fe₂O₃ and form photo-induced charge traps, promoting the separation of electron holes and enhancing the conductivity of Fe₂O₃. The other parts of -OH act as oxygen evolution catalysts to reduce the reaction obstacle of water oxidation and promote the transfer of holes to the electrode/electrolyte interface. The performance of FeOOH-Fe₂O₃ after plasma vacuum treatment has been greatly improved, and the photocurrent density is about 1.9 times higher than that of the Fe₂O₃ photoanode. The improvement in the water oxidation performance of PEC is considered to be the synergistic effect of the cocatalyst and oxygen vacancy. All outstanding PEC response characteristics show that the modification of the cocatalyst and oxygen vacancy doping represent a favorable strategy for synergistically improving Fe₂O₃ photoanode performance. Full article

Graphene quantum dots (GQDs) possess the photosensitive absorption for photoelectrochemical hydrogen evolution owing to special band structures, whereas they usually confront with photo-corrosion or undesired charge recombination during photoelectrochemical reactions. Hence, we establish the heterojunction between GQDs and MoSe₂ sheets via a hydrothermal process for improved stability and performance. Photoanodic water splitting with hydrogen evolution boosted by the heteroatom doped N,S-GQDs/MoSe₂ heterojunction has been attained due to the abundant active sites, promoted charge separation and transfer kinetics with reduced energy barriers. Diphasic 1T and 2H MoSe₂ sheet-hybridized quantum dots contribute to the Schottky heterojunction, which can play a key role in expedited carrier transport to inhibit accumulative photo-corrosion and increase photocurrent. Heteroatom dopants lead to favored energy band matching, bandgap narrowing, stronger light absorption and high photocurrent density. The external quantum efficiency of the doped heterojunction has been elevated twofold over that of the non-doped pristine heterojunction. Modification of the graphene quantum dots and MoSe₂ heterojunction demonstrate a viable and adaptable platform toward photoelectrochemical hydrogen evolution processes. Full article

The construction of semiconductor heterojunction photocatalysts that improve the separation and transfer of photoinduced charge carriers is an effective and widely employed strategy to boost photocatalytic performance. Herein, we have successfully constructed a CdS/Ag/Bi₂WO₆ Z-scheme heterojunction with an Ag-bridge as an effective charge transfer channel by a facile process. The heterostructure consists of both CdS and Ag nanoparticles anchored on the surface of Bi₂WO₆ nanosheets. The photocatalytic efficiency of the CdS/Ag/Bi₂WO₆ system was studied by the decontamination of tetracycline (TC) and Rhodamine B (RhB) under visible light irradiation (λ ≥ 420). The results exhibited that CdS/Ag/Bi₂WO₆ shows markedly higher photocatalytic performance than that of CdS, Bi₂WO₆, Ag/Bi₂WO₆, and CdS/Bi₂WO₆. The trapping experiment results verified that the ^•O₂⁻ and h⁺ radicals are the key active species. The results of photoluminescence spectral analysis and photocurrent responses indicated that the CdS/Ag/Bi₂WO₆ heterojunctions exhibit exceptional efficiency in separating and transferring photoinduced electron−hole pairs. Based on a series of characterization results, the boosted photocatalytic activity of the CdS/Ag/Bi₂WO₆ system is mostly due to the successful formation of the Ag-bridged Z-scheme heterojunction; these can not only inhibit the recombination rate of photoinduced charge carriers but also possess a splendid redox capacity. The work provides a way for designing a Z-scheme photocatalytic system based on Ag-bridged for boosting photocatalytic performance. Full article

A reported water-stable Zn-MOF ([Zn(L)₂(bpa)(H₂O)₂]·2H₂O, H₂L = 5-(2-cyanophenoxy) isophthalic acid has been prepared via a low-cost, general and efficient hydrothermal method. It is worth noting the structural features of Zn-MOF which exhibit the unsaturated metal site and the main non-covalent interactions including O⋯H, N⋯H and π-π stacking interactions, which lead to strong antibacterial and good tetracycline degradation ability. The average diameter of the Zn-MOF inhibition zone against Escherichia coli and Staphylococcus aureus was 12.22 mm and 10.10 mm, respectively. Further, the water-stable Zn-MOF can be employed as the effective photocatalyst for the photodegradation of tetracycline, achieving results of 67% within 50 min, and it has good cyclic stability. In addition, the photodegradation mechanism was studied using UV-vis diffuse reflection spectroscopy (UV-VIS DRS) and valence-band X-ray photoelectron spectroscopy (VB-XPS) combined with the ESR profile of Zn-MOF, which suggest that ·O₂⁻ is the main active species responsible for tetracycline photodegradation. Also, the photoelectric measurement results show that Zn-MOF has a good photocurrent generation performance under light. This provides us with a new perspective to investigate Zn-MOF materials as a suitable multifunctional platform for future environmental improvement applications. Full article

BiVO₄ is a highly promising material for Photoelectrochemical (PEC) water splitting photoanodes due to its narrow band gap value (~2.4 eV) and its ability to efficiently absorb visible light. However, the short hole migration distance, severe surface complexation, and low carrier separation efficiency limit its application. Therefore, in this paper, BiVO₄ was modified by loading CoOOH cocatalyst on the rare earth element Nd-doped BiVO₄ (Nd-BiVO₄) photoanode. The physical characterization and electrochemical test results showed that Nd doping will cause lattice distortion of BiVO₄ and introduce impurity energy levels to capture electrons to increase carrier concentration, thereby improving carrier separation efficiency. Further loading of surface CoOOH cocatalyst can accelerate charge separation and inhibit electron–hole recombination. Ultimately, the prepared target photoanode (CoOOH-Nd-BiVO₄) exhibits an excellent photocurrent density (2.4 mAcm⁻²) at 1.23 V versus reversible hydrogen electrode potential (vs. RHE), which is 2.67 times higher than that of pure BiVO₄ (0.9 mA cm⁻²), and the onset potential is negatively shifted by 214 mV. The formation of the internal energy states of rare earth metal elements can reduce the photoexcited electron–hole pair recombination, so as to achieve efficient photochemical water decomposition ability. CoOOH is an efficient and suitable oxygen evolution cocatalyst (OEC), and OEC decoration of BiVO₄ surface is of great significance for inhibiting surface charge recombination. This work provides a new strategy for achieving effective PEC water oxidation of BiVO₄. Full article

In this work, a series of chitosan (CS)-grafted carbon oxynitride (OCN) nanoparticles (denoted as CS-OCN) were successfully synthesized for the first time by thermal polycondensation and subsequent esterification. The structure and photocatalytic performance of CS-OCN nanoparticles were investigated. The XPS spectra of CS-OCN-3 showed the presence of amino bonds. The optimal photocatalytic degradation efficiency of the synthesized CS-OCN-3 could reach 94.3% within 390 min, while the photocurrent response intensity was about 150% more than that of pure OCN. The improved photocatalytic performance may be mainly attributed to the enhanced photogenerated carrier’s separation and transportation and stronger visible light response after CS grafting. In addition, the inhibition diameter of CS-OCN-3 reached 23 mm against E. coli within 24 h under visible light irradiation, exhibiting excellent photocatalytic bactericidal ability. The results of bacterial inhibition were supported by absorbance measurements (OD600) studies of E. coli. In a word, this work provided a rational design of an efficient novel metal-free photocatalyst to remove bacterial contamination and accelerate the degradation of organic dyes. Full article

A sensitive and selective label-free photoelectrochemical (PEC) immunosensor was designed for the detection of cardiac troponin I (cTnI). The platform was based on a fluorine-doped tin oxide (FTO)-coated glass photoelectrode modified with bismuth vanadate (BiVO₄) and sensitized by an electrodeposited bismuth sulfide (Bi₂S₃) film. The PEC response of the Bi₂S₃/BiVO₄/FTO platform for the ascorbic acid (AA) donor molecule was approximately 1.6-fold higher than the response observed in the absence of Bi₂S₃. The cTnI antibodies (anti-cTnI) were immobilized on the Bi₂S₃/BiVO₄/FTO platform surface to produce the anti-cTnI/Bi₂S₃/BiVO₄/FTO immunosensor, which was incubated in cTnI solution to inhibit the AA photocurrent. The photocurrent obtained by the proposed immunosensor presented a linear relationship with the logarithm of the cTnI concentration, ranging from 1 pg mL⁻¹ to 1000 ng mL⁻¹. The immunosensor was successfully employed in artificial blood plasma samples for the detection of cTnI, with recovery values ranging from 98.0% to 98.5%. Full article

In this work, a simple one-step hydrothermal method was employed to prepare the Ce-doped Fe₂O₃ ordered nanorod arrays (CFT). The Ce doping successfully narrowed the band gap of Fe₂O₃, which improved the visible light absorption performance. In addition, with the help of Ce doping, the recombination of electron/hole pairs was significantly inhibited. The external voltage will make the performance of the Ce-doped sample better. Therefore, the Ce-doped Fe₂O₃ has reached superior photoelectrochemical (PEC) performance with a high photocurrent density of 1.47 mA/cm² at 1.6 V vs. RHE (Reversible Hydrogen Electrode), which is 7.3 times higher than that of pristine Fe₂O₃ nanorod arrays (FT). The Hydrogen (H₂) production from PEC water splitting of Fe₂O₃ was highly improved by Ce doping to achieve an evolution rate of 21 μmol/cm²/h. Full article

CdS nanoparticles were constructed onto one-dimensional (1D) CeO₂ nanorods by a two-step hydrothermal method. The X-ray diffraction (XRD), transmission election microscopy (TEM), Raman spectra, X-ray photoelectron spectra (XPS) and UV-Vis diffuse reflection spectroscopy (DRS) techniques were used to characterize these CdS/CeO₂ nanocomposites. It was concluded that when the molar ratio of CdS and CeO₂ was 1:1, the nanocomposites exhibited the best photocatalytic desulfurization activity, reaching 92% in 3 h. Meanwhile, transient photocurrent (PT) measurement, photoluminescence (PL) spectra and electrochemical impedance spectroscopy (EIS) measurement indicated that the modification of CeO₂ nanorods by CdS nanoparticles could significantly inhibit the recombination of photogenerated electrons and holes. In addition, the possible mechanism of photocatalytic oxidation desulfurization of the nanocomposites was proposed. This study may provide an effective CeO₂-based photocatalyst for photocatalytic desulfurization applications. Full article

The tin dioxide (SnO₂) photocatalyst has a broad application prospect in the degradation of toxic organic pollutants. In this study, micron-sized spherical SnO₂ and flower indium oxide (In₂O₃) structures were prepared by a simple hydrothermal method, and the In₂O₃/SnO₂ composite samples were prepared by a “two-step method”. Using Rhodamine B (RhB) as a model organic pollutant, the photocatalytic performance of the In₂O₃/SnO₂ composites was studied. The photocurrent density of 1.0 wt.% In₂O₃/SnO₂ was twice that of pure SnO₂ or In₂O₃, and the degradation rate was as high as 97% after 240 min irradiation (87% after 120 min irradiation). The reaction rate was five times that of SnO₂ and nine times that of In₂O₃. Combined with the trapping experiment, the transient photocurrent response, and the corresponding characterization of active substances, the possible degradation mechanism was that the addition of In₂O₃ inhibited the efficiency of electron–hole pair recombination, accelerated the electron transfer and enhanced the photocatalytic activity. Full article

The preparation of clean energy is an effective way to solve the global energy crisis and reduce environmental pollution. The decomposition of water can produce hydrogen and oxygen, which is one of the effective ways to prepare clean energy. However, water oxidation is a bottleneck for water decomposition, thus, developing a water oxidation catalyst can accelerate the process of water decomposition to generate clean energy. Nickel-substituted polyoxometalate [Ni₂₅(H₂O)₂(OH)₁₈(CO₃)₂(PO₄)₆(SiW₉O₃₄)₆]⁵⁰⁻ (Ni25) is proven as an excellent water oxidation photocatalyst. To develop the effective photoelectrocatalyst for water oxidation, in this work, we constructed two composite films containing Ni25 on ITO, [PDDA/Ni25]_n, and PDDA/[Ni25/(PDDA–rGO)]_n, by layer-by-layer self-assembly, which is the first combination of nickel-substituted polyoxometalates and reduced graphene oxide (rGO). The study on the photoelectrocatalytic performance of the two films indicates that the water oxidation current of the film PDDA/[Ni25/(PDDA–rGO)]_n-modified electrode is increased by 33.7% after light irradiation, which is 1.71 times that of the film [PDDA/Ni25]_n-modified electrode. Moreover, the transient photocurrent response of the film PDDA/[Ni25/(PDDA–rGO)]_n-modified electrode demonstrates that there is a synergistic effect between rGO and Ni25, and rGO-accelerated electron transport and inhibited charge recombination. In addition, the film PDDA/[Ni25/(PDDA–rGO)]_n-modified electrode exhibits good stability, indicating its great potential as an effective photoelectrocatalyst for water oxidation in practical application. Full article

TiO₂ develops a higher efficiency when doping Bi into it by increasing the visible light absorption and inhibiting the recombination of photogenerated charges. Herein, a highly efficient Bi doped TiO₂ photoanode was fabricated via a one-step modified sol-gel method and a screen-printing technique for the anode of photocatalytic fuel cell (PFC). A maximum degradation rate of 91.2% of Rhodamine B (RhB) and of 89% after being repeated 5 times with only 2% lost reflected an enhanced PFC performance and demonstrated an excellent stability under visible-light irradiation. The excellent degradation performance was attributed to the enhanced visible-light response and decreased electron-hole recombination rate. Meanwhile, an excellent linear correlation was observed between the efficient photocurrent of PFC and the chemical oxygen demand of solution when RhB is sufficient. Full article

Monoclinic bismuth vanadate (BiVO₄) is an attractive material with which to fabricate photoanodes due to its suitable band structure and excellent photoelectrochemical (PEC) performance. However, the poor PEC stability originating from its severe photo-corrosion greatly restricts its practical applications. In this paper, pristine and Mo doped BiVO₄ ceramics were prepared using the spark plasma sintering (SPS) method, and their photoelectrochemical properties as photoanodes were investigated. The as-prepared 1% Mo doped BiVO₄ ceramic (Mo-BVO (C)) photoanode exhibited enhanced PEC stability compared to 1% Mo doped BiVO₄ films on fluorine doped Tin Oxide (FTO) coated glass substrates (Mo-BVO). Mo-BVO (C) exhibited a photocurrent density of 0.54 mA/cm² and remained stable for 10 h at 1.23 V vs. reversible hydrogen electrode (RHE), while the photocurrent density of the Mo-BVO decreased from 0.66 mA/cm² to 0.11 mA/cm² at 1.23 V vs. RHE in 4 h. The experimental results indicated that the enhanced PEC stability of the Mo-BVO (C) could be attributed to its higher crystallinity, which could effectively inhibit the dissociation of vanadium in BiVO₄ during the PEC process. This work may illustrate a novel ceramic design for the improvement of the stability of BiVO₄ photoanodes, and might provide a general strategy for the improvement of the PEC stability of metal oxide photoanodes. Full article

Cellulose nanomaterials have been widely investigated in the last decade, unveiling attractive properties for emerging applications. The ability of sulfated cellulose nanocrystals (CNCs) to guide the supramolecular organization of amphiphilic fullerene derivatives at the air/water interface has been recently highlighted. Here, we further investigated the assembly of Langmuir hybrid films that are based on the electrostatic interaction between cationic fulleropyrrolidines deposited at the air/water interface and anionic CNCs dispersed in the subphase, assessing the influence of additional negatively charged species that are dissolved in the water phase. By means of isotherm acquisition and spectroscopic measurements, we demonstrated that a tetra-sulfonated porphyrin, which was introduced in the subphase as anionic competitor, strongly inhibited the binding of CNCs to the floating fullerene layer. Nevertheless, despite the strong inhibition by anionic molecules, the mutual interaction between fulleropyrrolidines at the interface and the CNCs led to the assembly of robust hybrid films, which could be efficiently transferred onto solid substrates. Interestingly, ITO-electrodes that were modified with five-layer hybrid films exhibited enhanced electrical capacitance and produced anodic photocurrents at 0.4 V vs Ag/AgCl, whose intensity (230 nA/cm²) proved to be four times higher than the one that was observed with the sole fullerene derivative (60 nA/cm²). Full article