An Efficient MnO2 Photocathode with an Excellent SnO2 Electron Transport Layer for Photo-Accelerated Zinc Ion Batteries.

Photo-accelerated rechargeable batteries play a crucial role in fully utilizing solar energy, but it is still a challenge to fabricate dual-functional photoelectrodes with simultaneous high solar energy harvesting and storage. This work reports an innovative photo-accelerated zinc-ion battery (PAZIB) featuring a photocathode with a SnO2@MnO2 heterojunction. The design ingeniously combines the excellent electronic conductivity of SnO2 with the high energy storage and light absorption capacities of MnO2. The capacity of the SnO2@MnO2-based PAZIB is ≈598 mAh g-1 with a high photo-conversion efficiency of 1.2% under illumination at 0.1 A g-1, which is superior to that of most reported MnO2-based ZIB. The boosting performance is attributed to the synergistic effect of enhanced photogenerated carrier separation efficiency, improved conductivity, and promoted charge transfer by the SnO2@MnO2 heterojunction, which is confirmed by systematic experiments and theoretical simulations. This work provides valuable insights into the development of dual-function photocathodes for effective solar energy utilization.

Developing a Multifunctional Cathode for Photoassisted Lithium-Sulfur Battery.

Integration of solar cell and secondary battery cannot only promote solar energy application but also improve the electrochemical performance of battery. Lithium-sulfur battery (LSB) is an ideal candidate for photoassisted batteries owing to its high theoretical capacity. Unfortunately, the researches related the combination of solar energy and LSB are relatively lacking. Herein, a freestanding photoelectrode is developed for photoassisted lithium-sulfur battery (PALSB) by constructing a heterogeneous structured Au@N-TiO2 on carbon cloths (Au@N-TiO2/CC), which combines multiple advantages. The Au@N-TiO2/CC photoelectrode can produce the photoelectrons to facilitate sulfur reduction during discharge process, while generating holes to accelerate sulfur evolution during charge process, improving the kinetics of electrochemical reactions. Meanwhile, Au@N-TiO2/CC can work as an electrocatalyst to promote the conversion of intermediate polysulfides during charge/discharge process, mitigating induced side reactions. Benefiting from the synergistic effect of electrocatalysis and photocatalysis, PALSB assembled with an Au@N-TiO2/CC photoelectrode obtains ultrahigh specific capacity, excellent rate performance, and outstanding cycling performance. What is more, the Au@N-TiO2/CC assembled PALSB can be directly charged under light illumination. This work not only expands the application of solar energy but also provides a new insight to develop advanced LSBs.

Hydrophobic-treated yolk-shell SnS2@CSs Z-scheme confinement reactor for solar-electro-driven hydrogen peroxide production in neutral media.

The diffusion and adsorption properties of the O2/H2O corpuscles at active sites play a crucial role in the fast photo-electrocatalytic reaction of hydrogen peroxide (H2O2) production. Herein, SnS2 nanosheets with abundant interfacial boundaries and large specific areas are encapsulated into hollow mesoporous carbon spheres (CSs) with flexibility, producing a yolk-shell SnS2@CSs Z-scheme photocatalyst. The nanoconfined microenvironment of SnS2@CSs could enrich O2/H2O in catalyst cavities, which allows sufficient internal O2 transfer, improving the surface chemistry of catalytic O2 to O2- conversion and increasing reaction kinetics. By shaping the mixture of SnS2@CSs and polytetrafluoroethylene (PTFE) on carbon felt (CF) using the vacuum filtration method, the natural air-breathing gas diffusion photoelectrode (AGPE) was prepared, and it can achieve an accumulated concentration of H2O2 about 12 mM after a 10 h stability test from pure water at natural pH without using electrolyte and sacrificial agents. The H2O2 product is upgraded through one downstream route of conversion of H2O2 to sodium perborate. The improved H2O2 production performance could be ascribed to the combination of the confinement effect of SnS2@CSs and the rich triple phase interfaces with the continuous hydrophobic layer and hydrophilic layer to synergistically modulate the photoelectron catalytic microenvironment, which enhanced the transfer of O2 mass and offered a stronger affinity to oxygen bubbles. The strategy of combining the confined material with the air-breathing gas diffusion electrode equips a wide practical range of applications for the synthesis of high-yield hydrogen peroxide.

Subtraction Descriptors in Machine Learning for Optimizing the Cocatalyst Effect of Cobalt Phosphate on Hematite Photoanodes.

In the quest for sustainable energy solutions, the optimization of the photoelectrochemical (PEC) performance of hematite photoanodes through cocatalysts represents a promising avenue. This study introduces a novel machine learning approach, leveraging subtraction descriptors, to isolate and quantify the specific effects of cobalt phosphate (Co-Pi) as a cocatalyst on hematite's PEC performance. By integrating data from various analytical techniques, including photoelectrochemical impedance spectroscopy and ultraviolet-visible spectroscopy, with advanced machine learning models, we successfully predicted the PEC performance enhancement attributed to Co-Pi. The Gaussian process regression (GPR) model emerged as the most effective, revealing the critical influence of the interfacial resistance, bulk resistance, and interfacial capacitance on the PEC performance. These findings underscore the potential of cocatalysts in improving charge separation and extending charge carrier lifetimes, thereby boosting the efficiency of photocatalytic reactions. This study not only advances our understanding of the cocatalyst effect in photocatalytic systems but also demonstrates the power of machine learning in modifying complex materials and guiding the development of optimized photocatalytic materials. The implications of this research extend beyond hematite photoanodes, offering a generalizable framework for enhancing the photoelectrochemical properties of a wide range of material modifications such as cocatalyst deposition, doping, and passivation.

Dual Functionality of Surface States in Dictating Photocurrent Generation of Au Nanocluster-Sensitized TiO2 Electrodes.

Gold nanoclusters (Au NCs), composed of only a few atoms, exhibit molecule-like behavior due to their distinct electronic structures arising from quantum confinement effects. Unlike their plasmonic nanoparticle counterparts, these nonplasmonic Au NCs possess unique properties with significant potential for photosensitizer applications. While traditional and NC-based electrodes share architectural similarities, the photoelectrochemical (PEC) behavior of the latter diverges significantly. Sensitizing TiO2 with Au NCs introduces additional surface trap states. In contrast to conventional photosensitizers, where surface states typically have a negligible impact on hole transfer, these trap states actively mediate the charge transfer process in Au NC-sensitized TiO2 electrodes. In this study, we employed impedance spectroscopy to elucidate the role of surface trap states in photocurrent generation. Our investigation revealed that these states are critical in determining PEC performance, presenting a dichotomy: they facilitate charge transfer (enhancing PEC performance) while simultaneously promoting carrier recombination (limiting efficiency). We demonstrated that the judicious control of otherwise deleterious surface trap states can significantly boost photocurrent. Our findings highlight that the dual nature of surface trap states demands a comprehensive investigation to fully understand their intricate impact on PEC performance.

Charge Photoaccumulation in Covalent Polymer Networks for Boosting Photocatalytic Nitrate Reduction to Ammonia.

In the design of photoelectrocatalytic cells, a key element is effective photogeneration of electron-hole pairs to drive redox activation of catalysts. Despite recent progress in photoelectrocatalysis, experimental realization of a high-performance photocathode for multi-electron reduction of chemicals, such as nitrate reduction to ammonia, has remained a challenge due to difficulty in obtaining efficient electrode configurations for extraction of high-throughput electrons from absorbed photons. This work describes a new design for catalytic photoelectrodes using chromophore assembly-functionalized covalent networks for boosting eight-electron reduction of nitrate to ammonia. Upon sunlight irradiation, the photoelectrode stores a mass of reducing equivalents at the photoexcited chromophore assembly for multielectron reduction of a copper catalyst, enabling efficient nitrate reduction to ammonia. By introducing the new photoelectrode structure, it is demonstrated that the electronic interplay between charge photo-accumulating assembly and multi-electron redox catalysts can be optimized to achieve proper balance between electron transfer dynamics and thermodynamic output of photoelectrocatalytic systems.

Advancements in Transparent Conductive Oxides for Photoelectrochemical Applications.

Photoelectrochemical cells (PECs) are an important technology for converting solar energy, which has experienced rapid development in recent decades. Transparent conductive oxides (TCOs) are also gaining increasing attention due to their crucial role in PEC reactions. This review comprehensively delves into the significance of TCO materials in PEC devices. Starting from an in-depth analysis of various TCO materials, this review discusses the properties, fabrication techniques, and challenges associated with these TCO materials. Next, we highlight several cost-effective, simple, and environmentally friendly methods, such as element doping, plasma treatment, hot isostatic pressing, and carbon nanotube modification, to enhance the transparency and conductivity of TCO materials. Despite significant progress in the development of TCO materials for PEC applications, we at last point out that the future research should focus on enhancing transparency and conductivity, formulating advanced theories to understand structure-property relationships, and integrating multiple modification strategies to further improve the performance of TCO materials in PEC devices.

Particle-Based Photoelectrodes for PEC Water Splitting: Concepts and Perspectives.

This comprehensive review delves into the intricacies of the photoelectrochemical (PEC) water splitting process, specifically focusing on the design, fabrication, and optimization of particle-based photoelectrodes for efficient green hydrogen production. These photoelectrodes, composed of semiconductor materials, potentially harness light energy and generate charge carriers, driving water oxidation and reduction reactions. The versatility of particle-based photoelectrodes as a platform for investigating and enhancing various semiconductor candidates is explored, particularly the emerging complex oxides with compelling charge transfer properties. However, the challenges presented by many factors influencing the performance and stability of these photoelectrodes, including particle size, shape, composition, morphology, surface modification, and electrode configuration, are highlighted. The review introduces the fundamental principles of semiconductor photoelectrodes for PEC water splitting, presents an exhaustive overview of different synthesis methods for semiconductor powders and their assembly into photoelectrodes, and discusses recent advances and challenges in photoelectrode material development. It concludes by offering promising strategies for improving photoelectrode performance and stability, such as the adoption of novel architectures and heterojunctions.

High-Sensitivity Photoelectrochemical Ultraviolet Photodetector with Stable pH-Universal Adaptability Based on Whole Single-Crystal Integrated Self-Supporting 4H-SiC Nanoarrays.

Emerging photoelectrochemical (PEC) photodetectors (PDs) have notable advantages over conventional PDs and have attracted extensive attention. However, harsh liquid environments, such as those with high corrosivity and attenuation, substantially restrict their widespread application. Moreover, most PEC PDs are constructed by assembling numerous nanostructures on current collector substrates, which inevitably contain abundant interfaces and defects, thus greatly weakening the properties of PDs. To address these challenges, a high-performance pH-universal PEC ultraviolet (UV) PD based on a whole single-crystal integrated self-supporting 4H-SiC nanopore array photoelectrode is constructed, which is fabricated using a two-step anodic oxidation approach. The PD exhibits excellent photodetection behavior, with high responsivity (218.77 mA W-1), detectivity (6.64 × 1013 Jones), external quantum efficiency (72.47%), and rapid rise/decay times (17/48 ms) under 375 nm light illumination with a low intensity of 0.15 mW cm-2 and a bias voltage of 0.6 V, which is fall in the state-of-the-art of the wide-bandgap semiconductor-based PDs reported thus far. Furthermore, the SiC PEC PD exhibits excellent photoresponse and long-term operational stability in pH-universal liquid environments. The improved photodetection performance of the SiC PEC PD is primarily attributed to the synergistic effect of the nanopore array structure, integrated self-supporting configuration, and single-crystal structure of the whole photoelectrode.

Dissolution-Induced Surface Reconstruction of Ni0.95Pt0.05Si/p-Si Photocathode for Efficient Photoelectrochemical H2 Production.

Metal silicide/Si photoelectrodes have demonstrated significant potential for application in photoelectrochemical (PEC) water splitting to produce H2. To achieve an efficient and economical hydrogen evolution reaction (HER), a paramount consideration lies in attaining exceptional catalytic activity on the metal silicide surface with minimal use of noble metals. Here, this study presents the design and construction of a novel Ni0.95Pt0.05Si/p-Si photocathode. Dopant segregation is used to achieve a Schottky barrier height as high as 1.0 eV and a high photovoltage of 420 mV. To achieve superior electrocatalytic activity for HER, a dissolution-induced surface reconstruction (SR) strategy is proposed to in situ convert surface Ni0.95Pt0.05Si to highly active Pt2Si. The resulting SR Ni0.95Pt0.05Si/p-Si photocathode exhibits excellent HER performance with an onset potential of 0.45 V (vs RHE) and a high maximum photocurrent density of 40.5 mA cm-2 and a remarkable applied bias photon-to-current efficiency (ABPE) of 5.3% under simulated AM 1.5 (100 mW cm-2) illumination. The anti-corrosion silicide layer effectively protects Si, ensuring excellent stability of the SR Ni0.95Pt0.05Si/p-Si photoelectrode. This study highlights the potential for achieving efficient PEC HER using bimetallic silicide/Si photocathodes with reduced Pt consumption, offering an auspicious perspective for the cost-effective conversion of solar energy to chemical energy.

Molecular and Heterojunction Device Engineering of Solution-Processed Conjugated Reticular Oligomers: Enhanced Photoelectrochemical Hydrogen Evolution through High-Effective Exciton Separation.

Covalent organic frameworks (COFs) face limited processability challenges as photoelectrodes in photoelectrochemical water reduction. Herein, sub-10 nm benzothiazole-based colloidal conjugated reticular oligomers (CROs) are synthesized using an aqueous nanoreactor approach, and the end-capping molecular strategy to engineer electron-deficient units onto the periphery of a CRO nanocrystalline lattices (named CROs-Cg). This results in stable and processable "electronic inks" for flexible photoelectrodes. CRO-BtzTp-Cg and CRO-TtzTp-Cg expand the absorption spectrum into the infrared region and improve fluorescence lifetimes. Heterojunction device engineering is used to develop interlayer heterojunction and bulk heterojunction (BHJ) photoelectrodes with a hole transport layer, electron transport layer, and the main active layers, using a CROs/CROs-Cg or one-dimensional (1D) electron-donating polymer HP18 mixed solution via spinning coating. The ITO/CuI/CRO-TtzTp-Cg-HP18/SnO2/Pt photoelectrode shows a photocurrent of 94.9 µA cm‒2 at 0.4 V versus reversible hydrogen electrode (RHE), which is 47.5 times higher than that of ITO/Bulk-TtzTp. Density functional theory calculations show reduced energy barriers for generating adsorbed H* intermediates and increased electron affinity in CROs-Cg. Mott-Schottky and charge density difference analyses indicate enhanced charge carrier densities and accelerated charge transfer kinetics in BHJ devices. This study lays the groundwork for large-scale production of COF nanomembranes and heterojunction structures, offering the potential for cost-effective, printable energy systems.

Frontiers in Photoelectrochemical Catalysis: A Focus on Valuable Product Synthesis.

Photoelectrochemical (PEC) catalysis provides the most promising avenue for producing value-added chemicals and consumables from renewable precursors. Over the last decades, PEC catalysis, including reduction of renewable feedstock, oxidation of organics, and activation and functionalization of C─C and C─H bonds, are extensively investigated, opening new opportunities for employing the technology in upgrading readily available resources. However, several challenges still remain unsolved, hindering the commercialization of the process. This review offers an overview of PEC catalysis targeted at the synthesis of high-value chemicals from sustainable precursors. First, the fundamentals of evaluating PEC reactions in the context of value-added product synthesis at both anode and cathode are recalled. Then, the common photoelectrode fabrication methods that have been employed to produce thin-film photoelectrodes are highlighted. Next, the advancements are systematically reviewed and discussed in the PEC conversion of various feedstocks to produce highly valued chemicals. Finally, the challenges and prospects in the field are presented. This review aims at facilitating further development of PEC technology for upgrading several renewable precursors to value-added products and other pharmaceuticals.

Self-powered photoelectrochemical immunosensing platform for sensitive CEA detection using dual-photoelectrode synergistic signal amplification.

Self-powered photoelectrochemical (PEC) sensing, as an emerging sensing mode, can effectively solve the problems such as weak anti-interference ability and poor signal response of individual photoanode or photocathode sensing. In this work, an ITO/Co-CuInS2 photocathode and ITO/WO3@CdS photoanode based self-powered cathodic PEC immunosensor was developed, which integrated dual-photoelectrode to synergistic amplify the signal for highly sensitive and specific detection of carcinoembryonic antigen (CEA). The self-powered PEC sensor could drive electrons transfer through the difference in Fermi levels between the two photoelectrodes without an external bias voltage. The photoanode was introduced to amplify the photoelectric signal, and the photocathode was only designed for the construction of sensing interfaces. The proposed sensor quantitatively determined the target CEA with the detection limit of 0.23 pg/mL and a linear correlation confine of 0.1 pg/mL ∼100 ng/mL. The constructed immunosensing platform exhibited high sensitivity, satisfactory stability and great biological detection selectivity, providing a feasible and effective strategy for the manufacture of new self-powered sensors in high-performance PEC bioanalytical applications.

Recent Trends in Self-Powered Photoelectrochemical Sensors: From the Perspective of Signal Output.

Revolutionary developments in analytical chemistry have led to the rapid development of self-powered photoelectrochemical (PEC) sensors. Different from conventional PEC sensors, self-powered PEC sensors do not require an external power source or complex devices for the sensitive detection of targets. As a result, these sensors have enormous application potential for the development of novel portable sensors. An increasing body of work is making excellent progress toward the implementation of self-powered PEC sensors for detection, but there have been no reviews to date. The present review first introduces the state of the art in the development of self-powered PEC sensors. Then, different types of self-powered PEC sensors are summarized and discussed in detail, including their current, power, and potential. Additionally, single- and dual-photoelectrode systems are classified and systematically compared. Finally, the current developments and major challenges that need to be addressed are also summarized. This review provides valuable insights into the current state of self-powered PEC sensors to promote further progress in this field.

Progress in Promising Semiconductor Materials for Efficient Photoelectrocatalytic Hydrogen Production.

Photoelectrocatalytic (PEC) water decomposition provides a promising method for converting solar energy into green hydrogen energy. Indeed, significant advances and improvements have been made in various fundamental aspects for cutting-edge applications, such as water splitting and hydrogen production. However, the fairly low PEC efficiency of water decomposition by a semiconductor photoelectrode and photocorrosion seriously restrict the practical application of photoelectrochemistry. In this review, the mechanisms of PEC water decomposition are first introduced to provide a solid understanding of the PEC process and ensure that this review is accessible to a wide range of readers. Afterwards, notable achievements to date are outlined, and unique approaches involving promising semiconductor materials for efficient PEC hydrogen production, including metal oxide, sulfide, and graphite-phase carbon nitride, are described. Finally, four strategies which can effectively improve the hydrogen production rate-morphological control, doping, heterojunction, and surface modification-are discussed.

Identification of the Contributing Factors to the Photoelectric Conversion Efficiency for Hematite Photoanodes by Using Machine Learning.

Hematite has gained significant attention in the field of photocatalysis as one of the most promising materials for the photoanode of photoelectrochemical (PEC) water splitting due to visible light absorption and the abundance of availability. However, its performance improvement process suffers from a serious bottleneck due to "sample variation" and "inactivity". However, the physical origin of them has not yet been elucidated. To address these issues, we have developed a machine learning (ML) strategy using a combination of various analytical data of hematite photoanodes to discern "active/inactive" and identify the dominant factors. For the demonstration purpose of the ML strategy, we picked up one of the dominant factors, the interfacial resistivity between hematite and FTO, which has not generally been explored as a first candidate in the improvement of photocatalytic materials. The operational parameters for the sample preparation were optimized to modify the selected physical property. Along with the improvement of the selected resistivity, we found that the other dominant descriptors related to the properties of bulk hematite and the surface facet were also modified and help improve the PEC performance.

Computational-Guided Design of Photoelectrode Active Materials for Light-Assisted Energy Storage.

The design of a novel photoelectric integrated system is considered to be an efficient way to utilize and store inexhaustible solar energy. However, the mechanism of photoelectrode under illuminate conditions is still unclear. Density functional theory (DFT) provides standardized analysis and becomes a powerful way to explain the photoelectrochemical mechanism. Herein, the feasibility of four metal oxide configurations as photoelectrode materials by using a high throughput calculation method based on DFT are investigated. According to the photoelectrochemical properties, band structure and density of states are calculated, and the intercalate/deintercalate simulation is performed with adsorption configuration. The calculation indicates that the band gap of Fe2 CoO4 (2.404 eV) is narrower than that of Co3 O4 (2.553 eV), as well as stronger adsorption energy (-3.293 eV). The relationship between the electronic structure and the photoelectrochemical performance is analyzed and verified according to the predicted DFT results by subsequent experiments. Results show that the Fe2 CoO4 photoelectrode samples exhibit higher coulombic efficiency (97.4%) than that under dark conditions (94.9%), which is consistent with the DFT results. This work provides a general method for the design of integrated photoelectrode materials and is expected to be enlightening for the adjustment of light-assisted properties of multifunctional materials.

HCR/DNAzyme-triggered cascaded feedback cycle amplification for self-powered dual-photoelectrode detection of femtomolar HPV16.

For high-performance dual-photoelectrode assay, developing a pair of photoactive materials with well-matched band structure and the design of a powerful sensing strategy are highly desirable. Herein, the Zn-TBAPy pyrene-based MOF and BiVO4/Ti3C2 Schottky junction were employed as photocathode and photoanode to form an efficient dual-photoelectrode system. The integration of the cascaded hybridization chain reaction (HCR)/DNAzyme-assisted feedback amplification with DNA walker-mediated cycle amplification strategy realizes femtomolar HPV16 dual-photoelectrode bioassay. Through the activation of the HCR cascaded with the DNAzyme system in the presence of HPV16, plentiful HPV16 analogs are generated that leads to exponential positive feedback signal amplification. Meanwhile on the Zn-TBAPy photocathode, the NDNA hybridizes with the bipedal DNA walker followed by circular cleavage by Nb.BbvCI NEase, producing a dramatically enhanced PEC readout. The achieved ultralow detection limit of 0.57 fM and a wide linear range of 10-6 nM-103 nM showcase the excellent performance of the developed dual-photoelectrode system.

A dual-photoelectrode fuel cell-driven self-powered aptasensor based on the 1D/2D In2S3/MoS2@Fe-CNTs heterojunction for the ultrasensitive detection of Staphylococcus aureus.

A novel dual-electrode photo-fuel cell (PFC)-driven self-powered aptasensor was manufactured for the sensitive and selective detection of Staphylococcus aureus (S. aureus) using the one-dimensional (1D)/2D Schottky heterojunction comprising bimetallic indium/molybdenum sulfide nanosheets and iron-doped carbon nanotube (Fe-CNT) (denoted as In2S3/MoS2@Fe-CNTs) as the photocathode. Given the generation of a robust interface at In2S3/MoS2 and Fe-CNTs, the charge separation and transfer ability of photoexcited electron-hole pairs were enforced, thus improving the output voltage of the assembled PFC. In addition, the numerous active sites of the 1D/2D In2S3/MoS2@Fe-CNTs Schottky heterojunction enabled the immobilization of large amounts of aptamer. Accordingly, the proposed PFC-driven self-powered aptasensor exhibited a wide linear range in 10-1 × 107 CFU mL-1 with a detection limit of 1.2 CFU mL-1 toward S. aureus. High selectivity, excellent reproducibility, good stability, and acceptable regenerability, as well as great potential practicality, were also achieved for the detection of S. aureus using the developed PFC-driven self-powered aptasensor. This work not only provides a new photoactive material based on a robust 1D/2D Schottky heterojunction, but also constructs a novel PFC-based self-powered aptasensing strategy based on dual-photoelectrodes and with satisfactory performance for the detection of foodborne pathogens in diverse environments.

Dual-Functional Z-Scheme TiO2 @MoS2 @NC Multi-Heterostructures for Photo-Driving Ultrafast Sodium Ion Storage.

Exploiting dual-functional photoelectrodes to harvest and store solar energy is a challenging but efficient way for achieving renewable energy utilization. Herein, multi-heterostructures consisting of N-doped carbon coated MoS2 nanosheets supported by tubular TiO2 with photoelectric conversion and electronic transfer interfaces are designed. When a photo sodium ion battery (photo-SIB) is assembled based on the heterostructures, its capacity increases to 399.3 mAh g-1 with a high photo-conversion efficiency of 0.71 % switching from dark to visible light at 2.0 A g-1 . Remarkably, the photo-SIB can be recharged by light only, with a striking capacity of 231.4 mAh g-1 . Experimental and theoretical results suggest that the proposed multi-heterostructures can enhance charge transfer kinetics, maintain structural stability, and facilitate the separation of photo-excited carriers. This work presents a new strategy to design dual-functional photoelectrodes for efficient use of solar energy.