The reduced nicotinamide adenine dinucleotide (NADH) is a vital biomolecule involved in many biocatalytic processes, and the high cost makes it significant to regenerate NADH in vitro. The photoelectrochemical approach is a promising and environmentally friendly method for sustainable NADH regeneration. However, the free Rh-based mediator ([Cp*Rh (bpy)H2O]2+) in the electrolyte suffers from low efficiency due to the sluggish charge transfer controlled by the diffusion process. Herein, we report an efficient and facile covalent bonding of the Rh-based mediator with the Si-based photocathode for NADH regeneration. The bipyridine-containing covalent organic framework (BpyCOF) layer ensures the even distribution of mediators throughout the surface of the photoelectrode. The graphene interlayer provides a pathway for charge transport and prevents silicon from corrosion. Furthermore, during the synthesis of BpyCOF, it functions as a substrate to promote the growth of the oriented BpyCOF film. The imitated contact between the components of the photocathode favors the charge transfer to the surface to participate in a chemical reaction, thus improving the catalytic performance and the NADH regeneration efficiency, which is four times higher than the reported photocathode modified by the Rh-based mediator. This study offers a new strategy for the construction of photoelectrochemical solar energy conversion devices.

An essential step toward enabling the production of renewable and cost-efficient fuels is an improved understanding of the performance of energy conversion materials. In recent years, there has been growing interest in ternary metal oxides. Particularly, α-SnWO4 exhibited promising properties for application to photoelectrochemical (PEC) water splitting. However, the number of corresponding studies remains limited, and a deeper understanding of the physical and chemical processes in α-SnWO4 is necessary. To date, charge-carrier generation, separation, and transfer have not been exhaustively studied for SnWO4-based photoelectrodes. All of these processes depend on the phase composition, not only α-SnWO4 but also on the related phases SnW3O9 and WO3, as well as on their spatial distributions resulting from the coating synthesis. In the present work, these processes in different phases of tin tungstate films were investigated by transient surface photovoltage (TSPV) spectroscopy to complement the analysis of the applicability of α-SnWO4 thin films for practical PEC oxygen evolution. Pure α-SnWO4 films exhibit higher photoactivities than those of films containing secondary SnW3O9 and WO3 phases due to the higher recombination of charge carriers when these phases are present.

This study investigates the impact of intrinsic strain and phase transitions on the thermodynamic stability and electronic properties of Cu1-xAxAlO2 solid solutions, which are key to their photocatalytic performance. It is demonstrated that Cu1-xAxAlO2 with A = Ag, Au, Pt can form continuous isostructural solid solutions due to relatively small compressive strain, while a substantial increase strain restricts Cu1-xPdxAlO2 to forming only limited solutions. For A = Li, Na, the formation of heterostructural solid solutions is facilitated by structural motif alterations, accommodating significant differences in ionic radii and A-O bond characteristics. Specifically, Cu1-xLixAlO2 exhibits a phase transition at x ≈ 0.333, whereas Cu1-xNaxAlO2 undergoes three distinct phase transitions. Electronic structure analysis indicates that in Cu1-xAxAlO2 (A = Ag, Au), d10-d10 closed-shell interactions dominate, enabling tunable band gaps with varying solubility. Nevertheless, increased intrinsic strain in metal sublattices, as seen in A = Pd and Pt, shifts antibonding states to the Fermi level, inducing a semiconductor-to-metal transition. Experimental evidence confirms that Ag+ ions modulate the band gaps and carrier dynamics in Cu1-xAgxAlO2, with Cu0.75Ag0.25AlO2 exhibiting heightened photoelectrochemical activity and a 38.5-fold enhancement in H2 production rate over CuAlO2. Additionally, the coordination environment changes between alkali metals and O, induced by phase transitions, effectively tune the band edge positions and carrier dynamics of Cu1-xAxAlO2 (A = Li, Na) heterostructural solid solutions. Therefore, 3R-Cu0.97Li0.03AlO2 with asymmetric nonlinear dumbbell O-Cu-O demonstrates the highest photocatalytic H2 production activity, 72.9 times greater than CuAlO2. In contrast, α-Cu1-xAxAlO2 with a smaller CuO6 octahedral splitting energy exhibits increased band gaps, resulting in diminished photocatalytic activity. This research underscores that strain-driven phase transition provides an additional control factor and new mechanism for regulating the photo(electro)catalytic activity of Cu1-xAxAlO2 solid solutions.

Cyanobacteria play a crucial role in global carbon and nitrogen cycles through photosynthesis, making them valuable subjects for understanding the factors influencing their light utilization efficiency. Photosynthetic microorganisms offer a promising avenue for sustainable energy conversion in the field of photovoltaics. It was demonstrated before that application of an external electric field to the microbial biofilm or cell improves electron transfer kinetics and, consequently, efficiency of power generation. We have integrated live cyanobacterial cultures into photovoltaic devices by embedding Limnospira indica PCC 8005 cyanobacteria in agar and PEDOT:PSS matrices on the surface of boron-doped diamond electrodes. We have subjected them to varying external polarizations while simultaneously measuring current response and photosynthetic performance. For the latter, we employed Pulse-Amplitude-Modulation (PAM) fluorometry as a non-invasive and real-time monitoring tool. Our study demonstrates an improved light utilization efficiency for L. indica PCC 8005 when immobilized in a conductive matrix, particularly so for low-intensity light. Simultaneously, the impact of electrical polarization as an environmental factor influencing the photosynthetic apparatus diminishes as matrix conductivity increases. This results in only a slight decrease in light utilization efficiency for the illuminated sample compared to the dark-adapted state.

The exaltation of light-harvesting efficiency and the inhibition of fast charge recombination are pivotal to the improvement of photoelectrochemical (PEC) performance. Herein, a direct Z-scheme heterojunction is designed of Cu2S/CdIn2S4 by in situ growth of CdIn2S4 nanosheets on the surface of hollow CuS cubes and then annealing at 400 °C. The constructed Z-scheme heterojunction is demonstrated with electron paramagnetic resonance and redox couple (p-nitrophenol/p-aminophenol) measurements. Under illumination, it shows the photocurrent 6 times larger than that of hollow Cu2S cubes, and affords outstanding PEC performance over the known Cu2S and CdIn2S4-based photocatalysts. X-ray photoelectron spectroscopy and density functional theory results demonstrate a strong internal electric field formed in Cu2S/CdIn2S4 Z-scheme heterojunction, which accelerates the Z-scheme charge migration, thereby promoting electron-hole separation and enhancing their utilization efficiency. Moreover, the hollow structure of Cu2S is conducive to shortening the charge transport distance and improving light-harvesting capability. In proof-of-concept PEC application, a PEC detection method for miRNA-141 based on the sensitivity of benzo-4-chloro-hexadienone to light absorption on Cu2S/CdIn2S4 modified electrode is developed with good selectivity and a limit of detection of 32 aM. This work provides a simple approach for designing photoactive materials with highly efficient PEC performance.

The presence of persulfate (S2O82-) in decontamination processes favors the oxidation of organic pollutants due to its strong oxidation power. In this research we study the photoelectrochemical generation of persulfate using five mixed metal oxides electrodes (MMO) with different compositions and its effect on the degradation of sulfamethoxazole antibiotic (SMX) by photoelectrocatalysis (PEC) and electro-oxidation (EO). By PEC, all anodes generated a higher concentration of S2O82- than those not exposed to light. The high S2O82-concentration obtained by PEC was 0.150 mM using MMO[Ti/Ir/Ta] in a solution with Na2SO4 100 mM applying a current density of 2 mA/cm2. On the other hand, the maximum concentration obtained was 0.250 mM at 30 min of electrolysis for MMO[Ti/Ir/Ta] using Na2SO4 50 mM and applying current density of 5 mA/cm2. S2O82-production by EO was between 0.005 and 0.089 mM. It is observed that MMO based in Ta2O5 showed the best S2O82- production. The effect of S2O82- electro-generation (using the anode with the highest and the anode with the lowest S2O82- production) on the degradation of sulfamethoxazole by PEC and EO was studied using the experimental conditions with the best production of this oxidant. MMO[Ti/Ir/Ta] and MMO[Ti/Ru] were used as anodes, and it was observed that by PEC, 100% of SMX was degraded after 30 min of electrolysis using MMO[Ti/Ir/Ta] and 60 min using MMO[Ti/Ru]. By EO, the degradation of SMX was partial, demonstrating that the electrophotocatalytic effect favors the generation of S2O82-, enhancing the degradation of SMX at short electrolysis times.

The photoelectrocatalytic advanced oxidation process (PEAOP) necessitates high-performing and stable photoanodes for the effective oxidation of complex pollutants in industrial wastewater. This study presents the construction of 2D WO3/MXene heteronanostructures for the development of efficient and stable photoanode. The WO3/MXene heterostructure features well-ordered WO3 photoactive sites anchored on micron-sized MXene sheets, providing an increased visible light active catalytic surface area and enhanced electrocatalytic activities for pollutant oxidation. Phenol, a highly toxic compound, was completely oxidized at an applied potential of 0.8 V vs. RHE under visible light irradiation. Systematic optimization of operational conditions for the photoelectrocatalytic oxidation of phenol was conducted. The phenol oxidation mechanism was elucidated via high-performance liquid chromatography (HPLC) analysis and the identification of intermediate compounds. Additionally, a mixed model of phenol and arsenic (III) in polluted water demonstrated the capability of WO3/MXene photoanode for the simultaneous oxidation of both organic and inorganic pollutants, achieving complete conversion of phenol and As(III) to non-toxic As(V). The WO3/MXene photoanode facilitated water oxidation, generating a substantial amount of O2•- and •OH oxidative species, which are crucial for the concurrent oxidation of phenol and arsenic. Recyclability tests demonstrated a 99% retention of performance, confirming the WO3/MXene photoanode\'s suitability for long-term operation in PEAOPs. The findings suggest that integrating WO3/MXene photoanodes into water purification systems can enhance economic feasibility, reduce energy consumption, and improve efficiency. This PEAOP offers a viable solution to the critical issue of heavy metal and organic chemical pollution in various water bodies, given its scalability and ability to preserve ecosystems while conserving clean water resources.

Photoelectrochemical (PEC) technology is a promising approach for converting solar energy into chemical energy, offering significant potential for renewable energy applications. In this work, the CuO thin film was fabricated with different pH value in between 8.5 ± 0.1 and 10.5 ± 0.1 via Successive Ionic Layer Adsorption and Reaction (SILAR) method. The Effect of pH on thickness, structural, morphological, elemental composition and optical properties were investigated by using stylus profilometry, XRD, SEM, TEM, EDX, UV-vis and PL. The XRD results showed that as the pH increased, the crystallite size increased from 19.24 nm to 25.62 nm, with a monoclinic phase along the (111) direction. The CuO film deposited at pH value 10.5 ± 0.1 exhibit well defined identical particle with its size in the range between 200 and 300 nm was confirmed by SEM and TEM analysis. As the pH increased from 8.5 ± 0.1 to 10.5 ± 0.1, the CuO film bandgap (Eg) value reduced from 1.52 eV to 1.42 eV with indirect transition. The CuO photocathode deposited at pH 10.5 ± 0.1 shows maximum photocurrent density of 1.45 mA/cm2 at -0.1 V vs. RHE in 0.5 M Na2SO4 solution. Furthermore, the Electrochemical Impedance Spectroscopy (EIS) analysis shows, the CuO (pH 10.5 ± 0.1) electrode have higher conductivity value of 0.6862 S/cm compared CuO at pH 8.5 ± 0.1 (0.2779 S/cm) and CuO at pH 9.5 ± 0.1 (0.4646 S/cm) electrodes.

The influence of the ion transfer on photoinduced electron transfer (ET) reactions was studied on the surface of hyperbranched semiconducting BiVO4 particles spontaneously adsorbed at the liquid-liquid (L/L) interface between an aqueous LiCl solution and bis(triphenylphosphoranylidene) ammonium tetrakis(pentaflurophenyl)borate (BATB) in 1,2-dichlorethane. The organic electrolyte was supplemented with [Co(bpy)3](PF6)3 to accept photoexcited electrons from BiVO4 under formation of the corresponding Co(II) complex. The L/L interface was stabilized at the orifice of a micropipette (MP) and allowed to record ion transfer cyclic voltammetry (ITCV) by applying a Galvani potential difference Δ o w ϕ ${{\\rm{\\Delta }}_o^w \\varphi }$ between two reference electrodes in the electrolyte solutions with intermittent illumination by visible light (λ>420 nm). The photogenerated holes caused oxidation of water to O2. Co(II) and O2 were detected at constant Δ o w ϕ ${{\\rm{\\Delta }}_o^w \\varphi }$ at an amperometric microelectrode (ME) facing the orifice of the MP in either the organic or the aqueous electrolyte. The overall current exhibits a photocurrent only in the Δ o w ϕ ${{\\rm{\\Delta }}_o^w \\varphi }$ -range, in which the IT of PF6 - is kinetically limited. The amperometric detection of photogenerated products followed the same pattern as the photocurrent in the total current.

A biofunctional immunosensor combining photoelectrochemical (PEC) and electrochemical (EC) was proposed for the quantitative detection of the liver cancer marker alpha-fetoprotein (AFP) in human blood. BiVO4/BiOI-MWCNTs photoactive materials were first prepared on conductive glass FTO, and the photoelectrode was functionalized by chitosan and glutaraldehyde. Then, the AFP capture antibody (Ab1) was successfully modified on the photoelectrode, and the label-free rapid detection of AFP antigen was achieved by PEC. In addition, Au@PdPt nanospheres were also used as a marker for binding to AFP detection antibody (Ab2). Due to the excellent catalytic properties of Au@PdPt in EC reaction, a signal increase in the EC response can be achieved when Ab2 binds to the AFP antigen, which ensures high sensitivity for the detection of AFP. The detection limits of PEC and EC are 0.050 pg/mL and 0.014 pg/mL, respectively. The sensor also possesses good specificity, stability and reproducibility, shows excellent performance in the detection of clinical samples and has good clinical applicability.