Photoelectrochemical Response Research Articles

Photoelectrochemical detection of Cu2+ based on ZnIn2S4/WO3 Z-scheme heterojunction.

A one-step hydrothermal technique was utilized to generate WO3 nanosheets on fluorine-doped tin oxide (FTO) (WO3/FTO), which were subsequently modified with ZnIn2S4 microspheres to create a Z-scheme heterojunction ZnIn2S4/WO3/FTO electrode for Cu2+ detection. The heterojunction exhibited excellent photoelectric conversion efficiency, which was nearly 2.5-fold and 5.1-fold greater than that ofWO3 and ZnIn2S4. The reduced photoelectrochemical response signal was caused by the formation of CuxSandenabled Cu2+ assessment in water samples. After optimizing the experimental conditions, the anodic photocurrent at 0V vs SCE in 0.100M phosphate buffer (pH 7.0) containing 0.100M L-ascorbic acid was linear with the common logarithm of Cu2+ concentration from 5.00nM to 100μM, with a limit of detection of 1.2nM (S/N = 3). Satisfactory recovery results were obtained in the analyses of Xiangjiang River water samples.

In-situ cation-exchange deposited Ag2S/In4SnS8 of Z-type heterojunction coupled with DNA recycling amplification for photoelectrochemical biosensing

Herein, a novel photoelectrochemical (PEC) biosensor was developed utilizing an in situ cation-exchange method to deposit a high-performance Ag2S/In4SnS8, a Z-type heterojunction with co-shared S atoms, as a signal indicator and using DNA recycling amplification for the sensitive and accurate detection of miRNA-141. The photosensitive Ag2S deposited on the In4SnS8 surface not only facilitated the rapid generation of photoelectrons but also formed a Z-type heterojunction with In4SnS8, effectively inhibiting electron-hole pair recombination. This resulted in a considerable improvement in the photoelectric conversion efficiency of Ag2S/In4SnS8, yielding an ∼ 120-fold increase in photocurrent compared to that of In4SnS8 under 660-nm visible-light irradiation. Furthermore, the arborescent DNA structure formed by hybrid chain reaction (HCR) enhanced the steric effect, thereby reducing the PEC response. Importantly, numerous quenchers MnPP competed for light absorption and captured photogenerated electrons in the valence bands of In4SnS8 and Ag2S, reducing electron transfer to the electrode and further considerably reducing the photocurrent. This enabled the sensitive detection of miRNA-141 across a concentration range from 10 amol·L−1 to 100 pmol·L−1, with a limit of detection as low as 3.3 amol·L−1 (S/N = 3). The proposed biosensor exhibits excellent stability and is expected to be applied for detecting clinically relevant disease markers.

Plasmon-Enhanced Photoelectrochemistry of Photosystem II on a Hierarchical Tin Oxide Electrode for Ultrasensitive Detection of 17β-Estradiol.

Despite its excellent efficiency in natural photosynthesis, the utilization of photosystem II (PSII)-based artificial photoelectrochemical (PEC) systems for analytical purposes is hindered due to the low enzyme loading density and ineffective electron transfer (ET) processes. Here, we present a straightforward and effective approach to prepare a PSII-based biohybrid photoanode with remarkable photoresponse, enabled by the use of a hierarchically structured inverse-opal tin oxide (IO-SnO2) electrode combined with gold nanoparticles (Au NPs). The porous, carbon-containing IO-SnO2 structure allows for a high density and photoactivity loading of PSII complexes, while also providing strong electrical coupling between the protein film and the electrode. A new electron transfer pathway mediated by Au NPs was identified at the protein-electrode interface, which efficiently shuttles the photogenerated electrons from the enzyme to the IO-SnO2 electrode. Furthermore, the PEC response of the electrode was significantly enhanced by the surface plasmon resonance (SPR) effect of Au NPs. Upon light irradiation, this PSII-based photoanode exhibited an impressively high and stable photocurrent output, which was utilized to fabricate an aptasensor for 17β-Estradiol (E2) detection. Under optimal conditions, a detection limit of 0.33 pM was obtained, along with a broad detection range from 15 pM to 30 nM. The applicability of the aptasensor was assessed by measuring E2 in water and urine samples, demonstrating its feasibility in environmental monitoring and clinical tests.

Boron-doped TiO2 nanoparticles for improved photoelectrochemical response via enhanced surface area and visible light absorption

The present study introduces boron doping into TiO2 nanoparticles to synthesize boron-doped TiO2 samples. The structural and morphological properties of the pristine and doped samples are investigated using X-ray diffraction, Raman spectroscopy, Field Emission Scanning Electron Microscopy (FESEM) and High Resolution Transmission Electron Microscopy (HRTEM) techniques. Photoelectrochemical measurements have confirmed that a 3 wt % concentration of boron doped TiO2 nanoparticles shows improved photoelectrochemical response compared to pristine TiO2 nanoparticles. An ∼285-fold improvement (∼0.97 mA/cm2 at 0.81 V vs RHE) is observed in 3 wt % boron doped TiO2 nanoparticles array as compared to the pristine (3.4 μA/cm2 at 0.81 V vs RHE) photoanode samples. Moreover, the enhanced surface area, suppressed recombination, effective charge separation/transport of photogenerated charge carriers, and improved visible light absorption due to boron doping result in a remarkably high current density.

Anodic Synthesis of Highly Ordered TiO2 Nanotube Arrays: Role of Electrolyte Composition on the Structural, Morphological, Optical, and Photo-electrochemical Properties

The fluoride species present in two different anodizing electrolytes were used to produce TiO2 nanotube arrays (TiO2 NTAs) by simultaneous anodic reaction and chemical dissolution. In this investigation, two different electrolytes were used for the preparation; [Eth-TiO2 NAs: 95 ml ethylene glycol+0.5% NH4F+5 ml DI water] and [Gly-TiO2 NAs: 75 ml glycerine+0.5% NH4F+25 ml DI water]. The effects of the prepared electrolytes used in the synthesis of TiO2 nanotube arrays on structural element composition, morphology, and optical properties are the focus of this study and are characterized by X-ray diffraction (XRD), scanning electron microscopy field emission (FE-SEM), energy-dispersive X-ray spectroscopy (EDX) and UV-vis diffusion reflection spectroscopy (DRS), respectively. The photoelectrochemical properties of TiO2 NTAs prepared in different electrolytes were investigated. The photoelectrochemical performance of TiO2 NTAs in Na2SO3 (0.1 M) and Na2S (0.1) was examined under the light of 100 mW/cm2 from a xenon lamp. Comparing the photoelectrochemical (PEC) results of both electrolytes, we find that Eth-TiO2 NTAs contribute a wide surface area resulting in an enhanced PEC response. TiO2 NTs, which were prepared with Eth-TiO2 NTAs, exhibited the highest photocurrent density, 0.326 mA cm–2, and photoconversion efficiency (0.22%).

Preparation of PbS/TiO2 nanotube films for enhanced photoelectrochemical response and cathodic protection performance

Anodic oxidation method and sonication-assisted successive ionic layer adsorption and reaction (S-SILAR) process were used to prepare TiO2 nanotube films and PbS/TiO2 nanotube films. The effects of impregnation times on photoelectrochemical (PEC) performance of PbS/TiO2 nanotube films were systematically studied. The PEC properties were evaluated by UV–vis DRS, I-t, EIS and coupling potential. When PbS nanoparticles were impregnated for 15 times, the bandgap of PbS/TiO2 was narrowed to 1.4 eV, and the photocurrent density could reach 4.14 mA﹒cm−2, which increased by 12.8 times compared with TiO2. PbS nanoparticles loading onto TiO2 nanotube films is a simple and effective way to enhanced PEC response and cathodic protection performance.

Photoelectrochemical response of tin iodide phosphide (SnIP) composites with MoSe2, MoS2, and h‐BN

For a future world fuelled by green energy it is invaluable to develop, test and maximise the catalytic efficiency of new effective water‐splitting materials. In this paper, we further explore the catalytic activity of double‐helical tin iodide phosphide (SnIP), as it features bandgaps in the ideal region for this process. We found that its photoelectrochemical response can be multiplied by forming composites of SnIP with selected 2D materials, focusing on hexagonal boron nitride and the transition metal dichalcogenides (TMDs) MoSe2 and MoS2. These nanocomposites were analysed with Powder‐X‐ray diffraction (P‐XRD), Raman, and UV/VIS bandgap determination. Their photo activity was assessed under simulated solar light through chrono amperometry and linear sweep voltammetry (CA, LSV). The high anisotropy of the involved materials enables efficient charge separation at the 1D/2D interfaces, increasing photoelectrochemical response four‐fold.

Structural and optical investigation of Nb5+-doped Sn3O4 for photoelectrochemical hydrogen production

We report herein, the microwave-assisted hydrothermal (MAH) synthesis of Nb5+-doped Sn3O4 nanoparticles for the photoelectrochemical production of hydrogen (H2). Nb5+ ions inside the Sn3O4 created structural defects, contributing to a local structural disorder, as confirmed by micro-Raman spectra. Photoluminescence spectroscopy indicated the decrease of the violet-blue–green visible emission after adding Nb5+, revealing the formation of alternative energy pathways for the electron/hole recombination. Through the morphological analysis, it was observed that the Nb5+ dopant slightly changed the morphology of nano-petals in Sn3O4. We demonstrate that the 3 % Nb5+ doped-Sn3O4 photoanode presented higher charge carrier mobility, higher photocurrent density, and an impressive H2 production of 1.50 mmol L−1 in a 3 h experiment, compared to the pure Sn3O4 material. The best performance of the Nb5+ doped Sn3O4 nanomaterial could be ascribed to the formation of new energy levels in the Sn3O4 band gap, thereby inhibiting the electron-hole pair recombination and positively affecting the photoelectrochemical response of the doped material.

Research of two kinds of PANI@semiconductor based photocathodic coating corrosion protection effect and mechanism

PurposeThis study aims to report the development and experimental evaluation of two kinds of PANI@semiconductor based photocathodic anti-corrosion coating, for application on stainless steel substrates.Design/methodology/approachPANI was in situ chemical polymerized on TiO2 and BiVO4 particles, and FT-IR and SEM/EDS were used to understand the characteristics and elemental distribution of the composite particles. Composite coatings, which consisted of epoxy, PANI@TiO2 or PANI@BiVO4 and graphene, were prepared on the 304L stainless steel. Photoelectrochemical response measurement, electrochemical tests and immersion tests were used to assess the anti-corrosion performance of the prepared coatings in 45°C 3.5 wt.% NaCl solution. And the corrosion protection mechanism was further explained by combining with surface observation.FindingsThe photoelectrochemical response tests revealed the good photocathodic effect of the coatings, and the reversible oxidation-reduction properties of PANI (pseudocapacitive effect) leading to the repeated usage of the coatings. Consequently, the anti-corrosion mechanism of the composite coating is attributed to the physical barrier effect of the coating, the anodic protection effect of PANI and the photocathodic and energy store effect.Originality/valueThese kind coatings could prevent corrosion from day to night for stainless steel, which has great engineering application prospects on stainless steel corrosion protection.

CsPbBr3-based photoanode prepared by single-step Chemical vapor deposition of tunable thickness perovskite films

Cesium Lead Bromide (CsPbBr3) perovskite films have gained significant attention in photoelectrochemistry due to their promising properties. However, their widespread application necessitates scalable processing methods to produce high-quality films. Current techniques often involve post-synthesis steps to achieve desirable crystalline films or surface coverage for optimal performance. This research performed a single-step Chemical Vapor Deposition (CVD) approach to grow high-quality CsPbBr3 films. This methodology offers precise control over film thickness and grain orientation, crucial for optimizing photoelectrochemical response. The procedure simplifies fabrication by bypassing annealing or toxic solvent excess and growing films directly from CsPbBr3 crystals. Film thickness was controlled by adjusting growth time and precursor mass parameters to examine the photoelectrochemical performance across thicknesses ranging from 0.6 µm to 2.5 µm. Optimal results were achieved with dense, compact films 1.5 µm thick, which exhibited oriented grains along the (121) plane. Optical, structural, and morphological analyses confirmed a predominantly pure orthorhombic phase, although slight impurities were noted in thinner films. The 1.5 µm films showed a four-hour stable photocurrent of 6.2 mA/cm2 at 1.23 V versus reversible hydrogen electrode (RHE) under simulated solar conditions, underscoring their potential in advancing perovskite-based electrodes for efficient photoelectrochemical solar fuel generation.

Magnetic field-augmented photoelectrochemical water splitting in Co3O4 and NiO nanorod arrays

Effective charge separation is crucial for improving the sensitivity of photoelectrochemical studies. Here, we provide an immense magnetic field-based electron spin polarization approach for an efficient charge carrier separation. We have fabricated NiO and Co3O4 thin film and nanorod arrays by electron beam evaporation glancing angle method followed by annealing in a two-zone furnace. The photoelectrochemical performance was investigated for NiO and Co3O4 samples in the presence and absence of a magnetic field. The NiO and Co3O4 nanorods array samples exhibit better absorption compared with the thin film samples. The Co3O4 and NiO nanorod arrays showed the highest photocurrent density of 0.12 and 0.55 mA/cm2 in a magnetic field. The superior photoelectrochemical response of NiO and Co3O4 nanorods in a magnetic field could be ascribed to the limitation of non-radiative recombination of carriers manipulated by Lorentz force and spin polarization. Furthermore, the electrochemical impedance spectra of NiO and Co3O4 nanorod arrays in a magnetic field show the least charge transfer resistance. This study sheds light on the interaction process between external fields and radiative/non-radiative recombination of manipulating carriers. Thus, the application of a magnetic field presents an efficient and versatile approach to enhance the performance of photoelectrodes in solar water splitting.

Phosphomolybdates for Dual-Mode Photoelectrochemical Sensing toward Trace Chromium(VI) and Tetracycline.

Highly sensitive photoelectrochemical (PEC) sensors for trace carcinogens, such as heavy metal chromium(VI) [Cr(VI)] and antibiotic tetracycline (TC) are crucial. Herein, by integration of photoactive and redox phosphomolybdates with conjugated organic components, types of dual-mode PEC sensors were synthesized for sensing trace Cr(VI) and TC pollutants, with formulas of (H2bimb)2[Co2(bimb)1.5][Co(H2O)4][Co(P4Mo6O31H6)2]·6H2O (1), (H2bib)2[Co(H2O)3][Co2(H2O)5][Co(P4Mo6O31H6)2]·9H2O (2), and (H2bib)6[Co(Hbib)2(H2O)5][Co(P4Mo6O31H7)2]2·15H2O (3), where bimb represents 1,4-bis(1-imidazolyl)benzene and bib is 4,4'-bis(imidazolyl)bibphenyl. Hybrid 1 consisted of a three-dimensional framework structure constructed by Co{P4Mo6}2 clusters and one-dimensional (1D) {Co-bimb} chains, hybrid 2 exhibited 1D Co ion-bridged Co{P4Mo6}2 chains hydrogen-bonding with [H2bib]2+ cations, and hybrid 3 showed a discrete hybrid structure built upon a Co{P4Mo6}2 cluster modified by the {Co-bib} unit. Hybrids 1-3 displayed wide spectral absorption and excellent electrochemical redox properties, enabling dual-mode PEC responses to Cr(VI) reduction and TC oxidation. For Cr(VI) detection, hybrids 1-3 exhibited high sensitivities of 364.40, 225.72, and 124.29 μA·μM-1 as well as "nM" level detection limits (LODs) of 4.9, 10.0, and 11.0 nM, respectively. For TC detection, the sensitivities of hybrids 1-3 were 494.72, 308.78, and 174.03 μA·μM-1 and the LODs were 5.2, 6.1, and 12.9 nM, respectively. This research offers significant insights into designing efficient PEC sensors for the detection of environmental pollutants.

Sucrose-based reticulated vitreous carbon modified with N-doped TiO2 as an adsorbent and photocatalyst: Enhanced removal of methyl orange from aqueous solutions

A novel and low-cost 3D reticulated vitreous carbon (RVC) was synthesized and modified with (N-TiO2) to obtain an RVC/N-TiO2 composite, which was employed to remove methyl orange in an aqueous solution. This material was synthesized using the sacrificial template method and impregnated with an environmentally friendly sucrose resin, followed by N-TiO2 impregnation by dip-coating technique. SEM-EDS characterization confirmed the uniform covering of the TiO2, and XRD, Raman, and XPS evinced the presence of anatase and rutile polymorphs in the film and the N-doping, respectively. N-TiO2 coating onto RVC provides a higher specific surface area and electrochemical active area, boosting the wettability and the adsorption capacity. Additionally, this film favoured the photoelectrochemical response of the composite and the generation of •OH radicals. The adsorption, desorption, and photocatalytic studies demonstrated that >95 % decolorization of MO was achieved in 30 min without light irradiation and that >95.5 % degradation was attained in 120 min under visible light. The foam demonstrated reusability for over five cycles of adsorption/desorption of MO, with a capacity to recover up to 99 % of the dye after the first cycle and up to 94.07 % after the fifth cycle. Meanwhile, the minimal desorption of the dye (2.5 %) after illumination confirmed the photocatalytic degradation. This indicates that the process was not merely adsorption but also photocatalytic degradation.

Room-temperature electrodeposition of Cu2O layers and its low-temperature annealing for photoelectrochemical water splitting applications

Cuprous oxide layers were obtained on a conductive glass substrate via room-temperature electrochemical deposition from the electrolyte containing 0.4 M CuSO4, 3 M lactic acid (pH = 12) at −0.5 V vs. SCE for various durations (from 0.25 to 3 h). Physicochemical properties of as-received FTO/Cu2O materials were characterized using SEM, PXRD, and UV–Vis DRS. The photoelectrochemical (PEC) properties of the obtained electrodes were evaluated in detail by analyzing the influence of the energy of monochromatic radiation, and the applied polarization on the resulting photocurrent transients. It was found that Cu2O crystals are getting bigger and sharper with prolonged electrosynthesis duration and a slight decrease in the band gap energy from 2.4 to 2.1 eV with increasing deposition duration was observed. Moreover, this trend was also reflected in PEC properties of resulted material, higher photocurrents were generated by the material deposited for 3 h. More importantly, this PEC response was enhanced by low-temperature (100 °C, 200 °C) annealing. Thermal treatment at 100 °C led to a noticeable improvement in the photoactivity of the samples. Further increasing post-treatment temperature to 200 °C resulted in a further six-fold increase in photocurrents. Finally, the calculated values of accumulated and dissipated charges indicated significantly lower surface recombination after thermal treatment.

Synthesis of CuO nanosheets on Cu foil via one-step wet chemical process at different reaction temperatures and their photoelectrochemical performance

Cupric oxide (CuO) nanostructures were directly grown on copper substrate via a simple one step solution-immersion process. The films were formed by the direct oxidation of copper in aqueous solution containing sodium hydroxide (NaOH) and ammonium persulfate (NH4)2S2O8. The influence of the reaction temperature on the structural, morphological, optical and photoelectrochemical (PEC) properties of the formed copper compounds nanostructures was investigated. The XRD and Raman spectroscopy results revealed the formation of Cu(OH)2/CuO composite for the samples prepared at 3 and 25 °C, and pure CuO was obtained for the samples prepared at 45 and 55 °C. The SEM micrographs showed that the formed Cu(OH)2 and CuO present a nanowire bundles and nanosheet morphology, respectively. The increase of the reaction temperature enhanced the absorbance of the CuO samples in the entire visible region. According to the photoelectrochemical measurements, the increase of the reaction temperature resulted in an improvement of the PEC response. The CuO nanosheets synthesized at 55 °C presents the highest and the most stable PEC response. A reasonable mechanism describing the formation of nanostructured copper compounds at different reaction temperatures is discussed in this paper.

Spatial-resolved and self-calibrated 3D-printed photoelectrochemical biosensor engineered by multifunctional CeO2/CdS heterostructure for immunoassay

A spatial-resolved and self-calibrated photoelectrochemical (PEC) biosensor has been fabricated by a multifunctional CeO2/CdS heterostructure, achieving portable and sensitive detection of carcinoembryonic antigen (CEA) using a homemade 3D printing device. The CeO2/CdS heterostructure with matched band structure is prepared to construct the dual-photoelectrodes to improve the PEC response of CeO2. In particular, as the photoactive nanomaterial, the CeO2 also plays the role of peroxidase mimetic nanozymes. Therefore, the catalytic performance of CeO2 with different morphologies (e.g., nano-cubes, nano-rods and nano-octahedra) have been studied, and CeO2 nano-cubes (c-CeO2) achieve the optimal catalytic activity. Upon introducing CEA, the sandwich-type immunocomplex is formed in the microplate using GOx-AuNPs-labeled second antibody as detection antibody. As a result, H2O2 can be produced from the catalytic oxidization of glucose substrate by GOx, which is further catalyzed by CeO2 to form •OH, thus in situ etching CdS and decreasing the photocurrents. The self-calibration is achieved by the dual-channel photoelectrodes on the homemade 3D printing device to obtain the photocurrents ratio, thus effectively normalizing the fluctuations of external factors to enhance the accuracy. This integrated biosensor with a detection limit as low as 0.057 ng mL−1 provides a promising way for ultrasensitive immunoassay in clinic application in complex environments.

Boosting visible-light photoelectrochemical water splitting response of WO3–MoS2 nanocomposites by transition metal doping: Experimental and first-principles studies

The current study employs both theoretical and experimental methods to investigate the effect of Ti and Co doping on the WO3 nanocomposite with MoS2 photoanode's photoelectrochemical (PEC) water-splitting reaction. A simple hydrothermal and sol-gel method was adopted for the preparation of samples. The Ti-doped WO3–MoS2 (1.96 at %) sample showed the maximum optical absorption with a photocurrent density of 1.15 mA/cm2 at 1.6 V vs Ag/AgCl. The improvement in photocurrent density may be ascribed to the upward shifting of the conduction band edge towards the H+/H2 redox potential as well as the presence of a large number of active sites in MoS2. A high value of flat band potential of −0.3 V vs Ag/AgCl was achieved in Ti-doped WO3–MoS2, which was confirmed by Mott-Schottky measurements with the corresponding lowest charge transfer resistance at the semiconducting electrode/electrolyte interface. Furthermore, density functional theory calculations have also indicated that on doping WO3 with Ti and Co, there is a slight upward shift in the conduction band minimum, without any significant change in the valence band maximum, with respect to the Fermi level. This study provides new insight into the impact of transition metal doping and nanocomposite of chalcogenide materials for WO3-based PEC electrodes.

Photoelectrochemical sensor consisting of sulfhydryl-borate ester modified A1/B1 type Pillar[5]arene-functionalized gold NPs

Recognition of mitochondrial reactive oxygen species (ROS) in cells is essential for understanding the critical roles of different ROS in biology reaction processes. In this study, an ultrasensitive and specific photoelectrochemical (PEC) sensor is constructed and applied for the capture and identification of H2O2 in cells. For the targeted detection of H2O2 in cells containing similar groups, such as •OH and O2•-, a new sulfhydryl-borate ester modified A1/B1 type pillar[5]arene (BP5) with a specific borate group is designed as a specific recognition molecule, and Au nanoparticles (Au NPs) are synthesized as the photoactive material. Specifically, the localized surface plasmon resonance (LSPR) of the Au NPs and host-guest interaction between BP5 and H2O2 increase the photocurrent signal. At the same time, specific groups on BP5 react with H2O2 to specifically recognize it. The Au@BP5/GCE shows strong photoelectrochemical response for the detection of H2O2 with limit of detection (0.33 pM, S/N=3), an extended linear range (1–60 pM), high specificity, good stability and excellent reproducibility.

A Convenient In Situ Preparation of Cu2ZnSnS4-Anatase Hybrid Nanocomposite for Photocatalysis/Photoelectrochemical Water-Splitting Hydrogen Production.

This study details the rational design and synthesis of Cu2ZnSnS4 (CZTS)-doped anatase (A) heterostructures, utilizing earth-abundant elements to enhance the efficiency of solar-driven water splitting. A one-step hydrothermal method was employed to fabricate a series of CZTS-A heterojunctions. As the concentration of titanium dioxide (TiO2) varied, the morphology of CZTS shifted from floral patterns to sheet-like structures. The resulting CZTS-A heterostructures underwent comprehensive characterization through photoelectrochemical response assessments, optical measurements, and electrochemical impedance spectroscopy analyses. Detailed photoelectrochemical (PEC) investigations demonstrated notable enhancements in photocurrent density and incident photon-to-electron conversion efficiency (IPCE). Compared to pure anatase electrodes, the optimized CZTS-A heterostructures exhibited a seven-fold increase in photocurrent density and reached a hydrogen production efficiency of 1.1%. Additionally, the maximum H2 production rate from these heterostructures was 11-times greater than that of pure anatase and 250-times higher than the original CZTS after 2 h of irradiation. These results underscore the enhanced PEC performance of CZTS-A heterostructures, highlighting their potential as highly efficient materials for solar water splitting. Integrating Cu2ZnSnS4 nanoparticles (NPs) within TiO2 (anatase) heterostructures implied new avenues for developing earth-abundant and cost-effective photocatalytic systems for renewable energy applications.

Correlating activities and defects in (photo)electrocatalysts using in-situ multi-modal microscopic imaging

Photo(electro)catalysts use sunlight to drive chemical reactions such as water splitting. A major factor limiting photocatalyst development is physicochemical heterogeneity which leads to spatially dependent reactivity. To link structure and function in such systems, simultaneous probing of the electrochemical environment at microscopic length scales and a broad range of timescales (ns to s) is required. Here, we address this challenge by developing and applying in-situ (optical) microscopies to map and correlate local electrochemical activity, with hole lifetimes, oxygen vacancy concentrations and photoelectrode crystal structure. Using this multi-modal approach, we study prototypical hematite (α-Fe2O3) photoelectrodes. We demonstrate that regions of α-Fe2O3, adjacent to microstructural cracks have a better photoelectrochemical response and reduced back electron recombination due to an optimal oxygen vacancy concentration, with the film thickness and extended light exposure also influencing local activity. Our work highlights the importance of microscopic mapping to understand activity, in even seemingly homogeneous photoelectrodes.