The Impact of Electron Donating and Withdrawing Groups on Electrochemical Hydrogenolysis and Hydrogenation of Carbonyl Compounds.

The hydrogenolysis or hydrodeoxygenation of a carbonyl group, where the C═O group is converted to a CH2 group, is of significant interest in a variety of fields. A challenge in electrochemically achieving hydrogenolysis of a carbonyl group with high selectivity is that electrochemical hydrogenation of a carbonyl group, which converts the C═O group to an alcohol group (CH-OH), is demonstrated not to be the initial step of hydrogenolysis. Instead, hydrogenation and hydrogenolysis occur in parallel, and they are competing reactions. This means that although both hydrogenolysis and hydrogenation require adding H atoms to the carbonyl group, they involve different intermediates formed on the electrode surface. Thus, revealing the difference in intermediates, transition states, and kinetic barriers for hydrogenolysis and hydrogenation pathways is the key to understanding and controlling hydrogenolysis/hydrogenation selectivity of carbonyl compounds. In this study, we aimed to identify features of reactant molecules that can affect their hydrogenolysis/hydrogenation selectivity on a Zn electrode that was previously shown to promote hydrogenolysis over hydrogenation. In particular, we examined the electrochemical reduction of para-substituted benzaldehyde compounds with substituent groups having different electron donating/withdrawing abilities. Our results show a strikingly systematic impact of the substituent group where a stronger electron-donating group promotes hydrogenolysis and a stronger electron-withdrawing group promotes hydrogenation. These experimental results are presented with computational results explaining the substituent effects on the thermodynamics and kinetics of electrochemical hydrogenolysis and hydrogenation pathways, which also provide critically needed information and insights into the transition states involved with these pathways.

Halide Adsorption Enhances Electrochemical Hydrogenolysis of 5-Hydroxymethylfurfural by Suppressing Hydrogenation.

Reductive upgrading of 5-hydroxymethylfurfural (HMF), a biomass-derived platform molecule, to 2,5-dimethylfuran (DMF), a biofuel with an energy density 40% greater than that of ethanol, involves hydrogenolysis of both the aldehyde (C═O) and the alcohol (C-OH) groups of HMF. It is known that when hydrogenation of the aldehyde occurs to form 2,5-bis(hydroxymethyl)furan (BHMF), BHMF cannot be further reduced to DMF. Thus, aldehyde hydrogenation must be suppressed to increase the selectivity for DMF production. Previously, it was shown that on a Cu electrode hydrogenolysis occurs mainly through proton-coupled electron transfer (PCET), where a proton from the solution and an electron from the electrode are transferred to the organic species. In contrast, hydrogenation occurs not only through PCET but also through hydrogen atom transfer (HAT), where a surface-adsorbed hydrogen atom (H*) is transferred to the organic species. This study shows that halide adsorption on Cu can effectively suppress HAT by decreasing the steady-state H* coverage on Cu during HMF reduction. As HAT enables only aldehyde hydrogenation, a striking suppression of BHMF is observed, thereby enhancing DMF production. We discuss how the identity and concentration of the halide, along with the reduction conditions (i.e., potential and pH), affect halide adsorption on Cu and identify when optimal halide coverages are achieved to maximize DMF selectivity. Our experimental results are presented alongside computational results that elucidate how halide adsorption affects the adsorption energy of hydrogen and the steady-state H* coverage on Cu, which provide an atomic-level understanding of all experimentally observed effects.

C-C Bond Formation Coupled with C-C Bond Cleavage during Oxidative Upgrading of Glycerol on a Nanoporous BiVO4 Photoanode.

Production of biodiesel generates glycerol as a 10 wt% byproduct. Therefore, efficient and selective glycerol upgrading is critical for the sustainable production of biodiesel as well as for the production of chemicals from renewable feedstocks. In this study, the photoelectrochemical glycerol oxidation reaction (GOR) was investigated using a nanoporous BiVO4 photoanode in pH 9.3 and pH 2 buffer solutions. In both solutions, glycolaldehyde (GCAD), a C2 species, was the major product, which has never been the major product in any previous electrochemical or photoelectrochemical GOR study. To produce GCAD from the C3 species glycerol, C-C cleavage should occur to produce C2 and C1 species with a 1:1 ratio. Intriguingly, our results show that, during photoelectrochemical GOR on BiVO4, more GCAD is produced than can be explained by simple C-C cleavage, meaning that GCAD is also produced from C-C coupling of two C1 species produced from C-C cleavage. This is equivalent to converting two glycerol molecules to three GCAD molecules, which offers an extraordinary way to maximize GCAD production. To gain further insight into the nature of this unprecedented C-C coupling during GOR, photoelectrochemical oxidation of intermediate oxidation products (glyceraldehyde and 1,3-dihydroxyacetone) and glycerol-1,3-13C2 was compared to that of standard glycerol. Photoelectrochemical GOR was also compared with electrochemical GOR on BiVO4 to interrogate whether light is critical for the observed C-C coupling. Results obtained from comprehensive control experiments revealed critical information about C-C cleavage and C-C coupling during GOR on BiVO4.

Impact of Varying the Photoanode/Catalyst Interfacial Composition on Solar Water Oxidation: The Case of BiVO4(010)/FeOOH Photoanodes.

Photoanodes used in a water-splitting photoelectrochemical cell are almost always paired with an oxygen evolution catalyst (OEC) to efficiently utilize photon-generated holes for water oxidation because the surfaces of photoanodes are typically not catalytic for the water oxidation reaction. Suppressing electron-hole recombination at the photoanode/OEC interface is critical for the OEC to maximally utilize the holes reaching the interface for water oxidation. In order to explicitly demonstrate and investigate how the detailed features of the photoanode/OEC interface affect interfacial charge transfer and photocurrent generation for water oxidation, we prepared two BiVO4(010)/FeOOH photoanodes with different Bi:V ratios at the outermost layer of the BiVO4 interface (close to stoichiometric vs Bi-rich) while keeping all other factors in the bulk BiVO4 and FeOOH layers identical. The resulting two photoanodes show striking differences in the photocurrent onset potential and photocurrent density for water oxidation. The ambient pressure X-ray photoelectron spectroscopy results show that these two BiVO4(010)/FeOOH photoanodes show drastically different Fe2+:Fe3+ ratios in FeOOH both in the dark and under illumination with water, demonstrating the immense impact of the interfacial composition and structure on interfacial charge transfer. Using computational studies, we reveal the effect of the surface Bi:V ratio on the hydration of the BiVO4 surface and bonding with the FeOOH layer, which in turn affect the band alignments between BiVO4 and FeOOH. These results explain the atomic origin of the experimentally observed differences in electron and hole transfer and solar water oxidation performance of the two photoanodes having different interfacial compositions.

Influence of Excess Charge on Water Adsorption on the BiVO4(010) Surface.

We present a combined computational and experimental study of the adsorption of water on the Mo-doped BiVO4(010) surface, revealing how excess electrons influence the dissociation of water and lead to hydroxyl-induced alterations of the surface electronic structure. By comparing ambient pressure resonant photoemission spectroscopy (AP-ResPES) measurements with the results of first-principles calculations, we show that the dissociation of water on the stoichiometric Mo-doped BiVO4(010) surface stabilizes the formation of a small electron polaron on the VO4 tetrahedral site and leads to an enhanced concentration of localized electronic charge at the surface. Our calculations demonstrate that the dissociated water accounts for the enhanced V4+ signal observed in ambient pressure X-ray photoelectron spectroscopy and the enhanced signal of a small electron polaron inter-band state observed in AP-ResPES measurements. For ternary oxide surfaces, which may contain oxygen vacancies in addition to other electron-donating dopants, our study reveals the importance of defects in altering the surface reactivity toward water and the concomitant water-induced modifications to the electronic structure.

Integrating Computation and Experiment to Investigate Photoelectrodes for Solar Water Splitting at the Microscopic Scale.

ConspectusPhotoelectrochemical water-splitting is a promising and sustainable way to store the energy of the sun in chemical bonds and use it to produce hydrogen gas, a clean fuel. The key components in photoelectrochemical cells (PECs) are photoelectrodes, including a photocathode that reduces water to hydrogen gas and a photoanode that oxidizes water to oxygen gas. Materials used in photoelectrodes for PECs must effectively absorb sunlight, yield photogenerated carriers, and exhibit electronic properties that enable the efficient shuttling of carriers to the surface to participate in relevant water-splitting reactions. Discovering and understanding the key characteristics of optimal photoelectrode materials is paramount to the realization of PEC technologies.Oxide-based photoelectrodes can satisfy many of these materials requirements, including stability in aqueous environments, band edges with reasonable alignment with the redox potentials for water splitting, and ease of synthesis. However, oxide photoelectrodes generally suffer from poor charge transport properties and considerable bulk electron-hole separation, and they have relatively large band gaps. Numerous strategies have been proposed to improve these aspects and understand how these improvements are reflected in the photoelectrochemical performance. Unfortunately, the structural and compositional complexity of multinary oxides accompanied by the inherent complexity of photoelectrochemical processes makes it challenging to understand the individual effects of composition, structure, and defects in the bulk and on the surface on a material's photoelectrochemical properties. The integration of experiment and theory has great potential to increase our atomic-level understanding of structure-composition-property relationships in oxide photoelectrodes.In this Account, we describe how integrating experiment and theory is beneficial for achieving scientific insights at the microscopic scale. We highlight studies focused on understanding the role of (i) bulk composition via solid-state solutions, intercalation, and comparison with isoelectronic compounds, (ii) dopants for both the anion and cation and their interactions with oxygen vacancies, and (iii) surface/interface structure in the photocurrent generation and photoelectrochemical performance in oxide photoelectrodes. In each instance, we outline strategies and considerations for integrating experiment and theory and describe how this integration led to valuable insights and new directions in uncovering structure-composition-property relationships. Our aim is to demonstrate the unique value of combining experiment and theory in studying photoelectrodes and to encourage the continued effort to bring experiment and theory in closer step with each other.

Unraveling Two Pathways for Electrochemical Alcohol and Aldehyde Oxidation on NiOOH.

Selective oxidation of alcohols to their corresponding aldehyde or carboxylic acid is one of the most important classes of organic synthesis reactions. In addition, electrochemical alcohol oxidation is considered a viable anode reaction that can be paired with H2 evolution or other reductive fuel production reactions in electrochemical and photoelectrochemical cells. NiOOH, a material that has been extensively studied as an oxygen evolution catalyst, is among the most promising electrocatalysts for selective alcohol oxidation. Electrochemical alcohol oxidation by NiOOH has been understood since the 1970s to proceed through a hydrogen atom transfer to NiOOH. In this study, we establish that there is a second, more dominant general alcohol oxidation pathway on NiOOH enabled at more positive potentials. Using a three-step electrochemical procedure we developed, we deconvoluted the currents corresponding to these two pathways for various alcohols and aldehydes. The results show that alcohols and aldehydes have a distinct difference in their respective preferences for the two oxidation pathways. Our three-step electrochemical procedure also allowed us to evaluate the Ni valence involved with the different oxidation pathways to elucidate their mechanistic differences. Using these experimental results coupled with a computational investigation, we propose that the new pathway entails hydride transfer from the substrate to Ni4+ sites in NiOOH. This study offers an essential foundation to understand various oxidative electrochemical dehydrogenation reactions on oxide and hydroxide-based catalytic electrodes.

Progress on ternary oxide-based photoanodes for use in photoelectrochemical cells for solar water splitting.

Solar water splitting using photoelectrochemical cells (PECs) has emerged as one of the most promising routes to produce hydrogen as a clean and renewable fuel source. Among various semiconductors that have been considered as photoelectrodes for use in PECs, oxide-based photoanodes are particularly attractive because of their stability in aqueous media in addition to inexpensive and facile processing compared to other types of semiconductors. However, they typically suffer from poor charge carrier separation and transport. In the past few years, there has been tremendous progress in developing ternary oxide-based photoelectrodes, specifically, photoanodes. The use of ternary oxides provides more opportunities to tune the composition and electronic structure of the photoelectrode compared to binary oxides, thus providing more freedom to tune the photoelectrochemical properties. In this article, we outline the important characteristics to analyze when evaluating photoanodes and review the major recent progress made on the development of ternary oxide-based photoanodes. For each system, we highlight the favorable and unfavorable features and summarize the strategies utilized to address the challenges associated with each material. Finally, by combining our analyses of all the photoanodes surveyed in this review, we provide possible future research directions for each compound and an outlook for constructing more efficient oxide-based PECs. Overall, this review will provide a critical overview of current ternary oxide-based photoanodes and will serve as a platform for the design of future oxide-based PECs.

Perspectives on the Development of Oxide-Based Photocathodes for Solar Fuel Production.

Photoelectrochemical cells (PECs), which use semiconductor electrodes (photoelectrodes) to absorb solar energy and perform chemical reactions, constitute one of the most attractive strategies to produce chemical fuels using renewable energy sources. Oxide-based photoelectrodes specifically have been intensively investigated for the construction of PECs due to their relatively inexpensive processing costs and better stability in aqueous media compared with other types of photoelectrodes. Although there have been many advancements in the development of oxide-based photoanodes, our understanding of oxide-based photocathodes remains limited. The goal of this Perspective is to examine the recent progress made in the field of oxide-based photocathodes and discuss future research directions. The photocathode systems considered here include binary and ternary Cu-based photocathodes and ternary Fe-based photocathodes. We assessed the characteristics and major advantages and drawbacks of each system and identified the most critical research gaps. The insights and discussions provided in this Perspective will serve as useful resources for the design of future studies, leading to the development of more efficient and practical PECs.

Bismuth as a New Chloride-Storage Electrode Enabling the Construction of a Practical High Capacity Desalination Battery.

Materials that can selectively store Na and Cl ions in the bulk of their structures and release these ions with good cycle stability can enable the construction of a high capacity, rechargeable desalination cell for use in seawater desalination. In this study, the ability of a nanocrystalline Bi foam electrode to serve as an efficient and high capacity Cl-storage electrode using its conversion to BiOCl was investigated. When Bi as a Cl-storage electrode was coupled with NaTi2(PO4)3 as a Na-storage electrode, a new type of rechargeable desalination cell, which is charged during desalination and discharged during salination, was constructed. The resulting Bi-NaTi2(PO4)3 cell was tested under various salination and desalination conditions to investigate advantages and potential limitations of using Bi as a Cl-storage electrode. Slow Cl- release kinetics of BiOCl in neutral conditions and an imbalance in Cl and Na storage (i.e., Cl storage requires three electrons/Cl, while Na storage requires one electron/Na) were identified as possible drawbacks, but strategies to address these issues were developed. On the basis of these investigations, optimum desalination and salination conditions were identified where the Bi/NaTi2(PO4)3 cell achieved a desalination/salination cycle at ±1 mA cm-2 with a net potential input of only 0.20 V. The kinetics of Cl- release from BiOCl was significantly improved by the use of an acidic solution, and therefore, a divided cell was used for the salination process. We believe that with further optimizations the Bi/BiOCl electrode will enable efficient and practical desalination applications.

Electrochemical Growth of Copper Hydroxy Double Salt Films and Their Conversion to Nanostructured p-Type CuO Photocathodes.

New electrochemical synthesis methods were developed to produce copper hydroxy double salt(Cu-HDS) films with four different intercalated anions (NO3-, SO42-, Cl-, and dodecyl sulfate (DS)) as pure crystalline films as deposited (Cu2NO3(OH)3, Cu4SO4(OH)6, Cu2Cl(OH)3, and Cu2DS(OH)3). These methods are based on p-benzoquinone reduction, which increases the local pH at the working electrode and triggers the precipitation of Cu2+ and appropriate anions as Cu-HDS films on the working electrode. The resulting Cu-HDS films could be converted to crystalline Cu(OH)2 and CuO films by immersing them in basic solutions. Because Cu-HDS films were composed of 2D crystals as a result of the atomic-level layered structure of HDS, the CuO films prepared from Cu-HDS films have unique low-dimensional nanostructures, creating high surface areas that cannot be obtained by direct deposition of CuO, which has a 3D atomic-level crystal structure. The resulting nanostructures allowed the CuO films to facilitate electron-hole separation and demonstrate great promise for photocurrent generation when investigated as a photocathode for a water-splitting photoelectrochemical cell. Electrochemical synthesis of Cu-HDS films and their facile conversion to CuO films will provide new routes to tune the morphologies and properties of the CuO electrodes that may not be possible by other synthesis means.

Electrochemical Synthesis of Photoelectrodes and Catalysts for Use in Solar Water Splitting.

This review focuses on introducing and explaining electrodepostion mechanisms and electrodeposition-based synthesis strategies used for the production of catalysts and semiconductor electrodes for use in water-splitting photoelectrochemical cells (PECs). It is composed of three main sections: electrochemical synthesis of hydrogen evolution catalysts, oxygen evolution catalysts, and semiconductor electrodes. The semiconductor section is divided into two parts: photoanodes and photocathodes. Photoanodes include n-type semiconductor electrodes that can perform water oxidation to O2 using photogenerated holes, while photocathodes include p-type semiconductor electrodes that can reduce water to H2 using photoexcited electrons. For each material type, deposition mechanisms were reviewed first followed by a brief discussion on its properties relevant to electrochemical and photoelectrochemical water splitting. Electrodeposition or electrochemical synthesis is an ideal method to produce individual components and integrated systems for PECs due to its various intrinsic advantages. This review will serve as a good resource or guideline for researchers who are currently utilizing electrochemical synthesis as well as for those who are interested in beginning to employ electrochemical synthesis for the construction of more efficient PECs.

Electrochemical Synthesis of Highly Oriented, Transparent, and Pinhole-Free ZnO and Al-Doped ZnO Films and Their Use in Heterojunction Solar Cells.

Electrochemical synthesis conditions using nonaqueous solutions were developed to prepare highly transparent (T > 90%) and crystalline ZnO and Al-doped ZnO (AZO) films for use in solar energy conversion devices. A focused effort was made to produce pinhole-free films in a reproducible manner by identifying a key condition to prevent the formation of cracks during deposition. The polycrystalline domains in the resulting films had a uniform orientation (i.e., the c-axis perpendicular to the substrate), which enhanced the electron transport properties of the films. Furthermore, electrochemical Al doping of ZnO using nonaqueous media, which was demonstrated for the first time in this study, effectively increased the carrier density and raised the Fermi level of ZnO. These films were coupled with an electrodeposited p-type Cu2O to construct p-n heterojunction solar cells to demonstrate the utilization of these films for solar energy conversion. The resulting n-ZnO/p-Cu2O and n-AZO/p-Cu2O cells showed excellent performance compared with previously reported n-ZnO/p-Cu2O cells prepared by electrodeposition. In particular, replacing ZnO with AZO resulted in simultaneous enhancements in short circuit current and open circuit potential, and the n-AZO/p-Cu2O cell achieved an average power conversion efficiency (η) of 0.92 ± 0.09%. The electrodeposition condition reported here will offer a practical and versatile way to produce ZnO or AZO films, which play key roles in various solar energy conversion devices, with qualities comparable to those prepared by vacuum-based techniques.

Electrochemical Synthesis of Binary and Ternary Niobium-Containing Oxide Electrodes Using the p-Benzoquinone/Hydroquinone Redox Couple.

New electrochemical synthesis methods have been developed to obtain layered potassium niobates, KNb3O8 and K4Nb6O17, and perovskite-type KNbO3 as film-type electrodes. The electrodes were synthesized from aqueous solutions using the redox chemistry of p-benzoquinone and hydroquinone to change the local pH at the working electrode to trigger deposition of desired phases. In particular, the utilization of electrochemically generated acid via the oxidation of hydroquinone for inorganic film deposition was first demonstrated in this study. The layered potassium niobates could be converted to (H3O)Nb3O8 and (H3O)4Nb6O17 by cationic exchange, which, in turn, could be converted to Nb2O5 by heat treatment. The versatility of the new deposition method was further demonstrated for the formation of CuNb2O6 and AgNbO3, which were prepared by the deposition of KNb3O8 and transition metal oxides, followed by thermal and chemical treatments. Considering the lack of solution-based synthesis methods for Nb-based oxide films, the methods reported in this study will contribute greatly to studies involving the synthesis and applications of Nb-based oxide electrodes.

Marked enhancement in electron-hole separation achieved in the low bias region using electrochemically prepared Mo-doped BiVO4 photoanodes.

Mo-doped BiVO4 electrodes were prepared by an electrochemical route for use as photoanodes in a photoelectrochemical cell. The purpose of Mo-doping was to improve the electron transport properties, which in turn can increase the electron-hole separation yield. The poor electron-hole separation yield was known to be one of the main limiting factors for BiVO4-based photoanodes. The electrochemical route provided an effective way of doping BiVO4, and the optimally doped sample, BiV(0.97)Mo(0.03)O4, increased the electron-hole separation yield from 0.23 to 0.57 at 0.6 V vs. RHE, which is a record high separation yield achieved for BiVO4-based photoanodes. As a result, BiV(0.97)Mo(0.03)O4 generated impressive photocurrents, for example, 2 mA cm(-2) at a potential as low as 0.4 V vs. RHE for sulfite oxidation, which has fast oxidation kinetics and, therefore, the loss of holes by surface recombination is negligible. For photooxidation of water, BiV(0.97)Mo(0.03)O4 was paired with FeOOH as an oxygen evolution catalyst (OEC) to improve the poor catalytic ability of BiV(0.97)Mo(0.03)O4 for water oxidation. The resulting BiV(0.97)Mo(0.03)O4/FeOOH photoanodes generated a significantly improved photocurrent for water oxidation compared to previous reported results, but the photocurrent of BiV(0.97)Mo(0.03)O4/FeOOH for water oxidation could not reach the photocurrent of BiV(0.97)Mo(0.03)O4 for sulfite oxidation. In order to examine the cause, the effects of Mo-doping on the interaction between BiVO4 and FeOOH and the effects of FeOOH on the electron-hole separation yield of BiV(0.97)Mo(0.03)O4 were investigated in detail, which provided new insights into semiconductor-OEC interactions.

Progress in bismuth vanadate photoanodes for use in solar water oxidation.

Harvesting energy directly from sunlight as nature accomplishes through photosynthesis is a very attractive and desirable way to solve the energy challenge. Many efforts have been made to find appropriate materials and systems that can utilize solar energy to produce chemical fuels. One of the most viable options is the construction of a photoelectrochemical cell that can reduce water to H(2) or CO(2) to carbon-based molecules. Bismuth vanadate (BiVO(4)) has recently emerged as a promising material for use as a photoanode that oxidizes water to O(2) in these cells. Significant advancement in the understanding and construction of efficient BiVO(4)-based photoanode systems has been made within a short period of time owing to various newly developed ideas and approaches. In this review, the crystal and electronic structures that are closely related to the photoelectrochemical properties of BiVO(4) are described first, and the photoelectrochemical properties and limitations of BiVO(4) are examined. Subsequently, the latest efforts toward addressing these limitations in order to improve the performances of BiVO(4)-based photoanodes are discussed. These efforts include morphology control, formation of composite structures, composition tuning, and coupling oxygen evolution catalysts. The discussions and insights provided in this review reflect the most recent approaches and directions for general photoelectrode developments and they will be directly applicable for the understanding and improvement of other photoelectrode systems.

Efficient and stable photo-oxidation of water by a bismuth vanadate photoanode coupled with an iron oxyhydroxide oxygen evolution catalyst.

BiVO(4) films were prepared by a simple electrodeposition and annealing procedure and studied as oxygen evolving photoanodes for application in a water splitting photoelectrochemical cell. The resulting BiVO(4) electrodes maintained considerable photocurrent for photo-oxidation of sulfite, but generated significantly reduced photocurrent for photo-oxidation of water to oxygen, also decaying over time, suggesting that the photoelectrochemical performance of BiVO(4) for water oxidation is mainly limited by its poor catalytic ablity to oxidize water. In order to improve the water oxidation kinetics of the BiVO(4) electrode, a layer of FeOOH was placed on the BiVO(4) surface as an oxygen evolution catalyst using a new photodeposition route. The resulting BiVO(4)/FeOOH photoanode exhibitied significantly improved photocurrent and stability for photo-oxidation of water, which is one of the best among all oxide-based phoatoanode systems reported to date. In particular, the BiVO(4)/FeOOH photoanode showed an outstanding performance in the low bias region (i.e., E < 0.8 V vs RHE), which is critical in determining the overall operating current density when assembling a complete p-n photoelectrochemical diode cell. The photocurrent-to-O(2) conversion efficiency of the BiVO(4)/FeOOH photoanode is ca. 96%, confirming that the photogenerated holes in the BiVO(4)/FeOOH photoanode are indeed excusively used for O(2) evolution.

Junction studies on electrochemically fabricated p-n Cu(2)O homojunction solar cells for efficiency enhancement.

p-n Cu(2)O homojunction solar cells were electrochemically fabricated by consecutively depositing an n-Cu(2)O layer on a p-Cu(2)O layer. In order to better understand the Fermi levels of the electrochemically grown polycrystalline p- and n-Cu(2)O layers and maximize the overall cell performance, the back and front contacts of the Cu(2)O homojunction cells were systematically changed and the I-V characteristics of the resulting cells were examined. The result shows that the intrinsic doping levels of the electrochemically prepared p-Cu(2)O and n-Cu(2)O layers are very low and they made almost Ohmic junctions with Cu metal with which previously studied p-Cu(2)O layers prepared by thermal oxidation of Cu foils are known to form Schottky junctions. The best cell performance (an η of 1.06%, a V(OC) of 0.621 V, an I(SC) of 4.07 mA cm(-2), and a fill factor (ff) of 42%) was obtained when the p-Cu(2)O layer was deposited on a commercially available ITO substrate as the back contact and a sputter deposited ITO layer was used as the front contact on the n-Cu(2)O layer. The unique features of the p-n Cu(2)O homojunction solar cell are discussed in comparison with other Cu(2)O-based heterojunction solar cells.

Photochemical deposition of cobalt-based oxygen evolving catalyst on a semiconductor photoanode for solar oxygen production.

This study describes the photochemical deposition of Co-based oxygen evolution catalysts on a semiconductor photoanode for use in solar oxygen evolution. In the photodeposition process, electron-hole pairs are generated in a semiconductor upon illumination and the photogenerated holes are used to oxidize Co(2+) ions to Co(3+) ions, resulting in the precipitation of Co(3+)-based catalysts on the semiconductor surface. Both photodeposition of the catalyst and solar O(2) evolution are photo-oxidation reactions using the photogenerated holes. Therefore, photodeposition provides an efficient way to couple oxygen evolution catalysts with photoanodes by naturally placing catalysts at the locations where the holes are most readily available for solar O(2) evolution. In this study Co-based catalysts were photochemically deposited as 10-30 nm nanoparticles on the ZnO surface. The comparison of the photocurrent-voltage characteristics of the ZnO electrodes with and without the presence of the Co-based catalyst demonstrated that the catalyst generally enhanced the anodic photocurrent of the ZnO electrode with its effect more pronounced when the band bending is less significant. The presence of Co-based catalyst on the ZnO photoanode also shifted the onset potential of the photocurrent by 0.23 V to the negative direction, closer to the flat band potential. These results demonstrated that the cobalt-based catalyst can efficiently use the photogenerated holes in ZnO to enhance solar O(2) evolution. The photodeposition method described in this study can be used as a general route to deposit the Co-based catalysts on any semiconductor electrode with a valence band edge located at a more positive potential than the oxidation potential of Co(2+) ions.