Understanding the origin of photoelectrode performance enhancement by probing surface kinetics.
ABSTRACT: Photoelectrochemical (PEC) water splitting holds the potential to meet the challenges associated with the intermittent nature of sunlight. Catalysts have often been shown to improve the performance of PEC water splitting, but their working mechanisms are not well understood. Using intensity modulated photocurrent spectroscopy (IMPS), we determined the rate constants of water oxidation and recombination at the surface of three different hematite-based photoanodes. It was found that the best performing electrodes, in terms of photocurrent onset potential, exhibited the slowest water oxidation rate constants, which was a surprise. The performance of these photoelectrodes was enabled by the slow surface recombination. When amorphous NiFeO x , a water oxidation catalyst, was present, the rate of surface hole transfer actually slowed down; what was slowed more was the recombination rate at the hematite surface, resulting in better water oxidation performance. As such, NiFeO x primarily serves as a passivation layer rather than a catalytic layer. Together a better understanding of the role of catalytic overlayers for water oxidation has been achieved.
Project description:Hematite has a great potential as a photoanode for photoelectrochemical (PEC) water splitting by converting solar energy into hydrogen fuels, but the solar-to-hydrogen conversion efficiency of state-of-the-art hematite photoelectrodes are still far below the values required for practical hydrogen production. Here, we report a core-shell formation of gradient tantalum-doped hematite homojunction nanorods by combination of hydrothermal regrowth strategy and hybrid microwave annealing, which enhances the photocurrent density and reduces the turn-on voltage simultaneously. The unusual bi-functional effects originate from the passivation of the surface states and intrinsic built-in electric field by the homojunction formation. The additional driving force provided by the field can effectively suppress charge-carrier recombination both in the bulk and on the surface of hematite, especially at lower potentials. Moreover, the synthesized homojunction shows a remarkable synergy with NiFe(OH)<sub>x</sub> cocatalyst with significant additional improvements of photocurrent density and cathodic shift of turn-on voltage. The work has nicely demonstrated multiple collaborative strategies of gradient doping, homojunction formation, and cocatalyst modification, and the concept could shed light on designing and constructing the efficient nanostructures of semiconductor photoelectrodes in the field of solar energy conversion.
Project description:While bismuth vanadate (BiVO4) has emerged as a promising photoanode in solar water splitting, it still suffers from poor electron-hole separation and electron transport properties. Therefore, the development of BiVO4 nanomaterials that enable performing high charge transfer rate at the interface and lowering charge recombination is urgent needed. Herein, cobalt borate (Co-B) nanoparticle arrays anchored on electrospun W-doped BiVO4 porous nanotubes (BiV0.97W0.03O4) was prepared for photoelectrochemical (PEC) water oxidation. One-dimensional, free-standing and porousBiV0.97W0.03O4/Co-B nanotubes was synthesized through electrospun and electrodeposition process. BiV0.97W0.03O4/Co-B arrays exhibit a unique self-supporting core-shell structure with rough porous surface, providing abundant conductive cofactor (W) and electrochemically active sites (Co) exposed to the electrolyte. When applied to PEC water oxidation. BiV0.97W0.03O4/Co-B modified FTO electrode displays high incident photon-to-current conversion efficiency (IPCE) of 33% at 405 nm (at 1.23 V vs. RHE) and its photocurrent density is about 4 times to the pristine nanotube. The higher PEC water oxidation properties of BiV0.97W0.03O4/Co-B porous nanotubes may be attributed to the effectively suppress the electron-hole recombination at electrolyte interface due to its self-supporting core-shell structure, the high electrocatalytic activity of Co and the good electrical conductivity of BiV0.97W0.03O4 arrays. This work offers a simple preparation strategy for the integrated Co-B nanoparticle with BiV0.97W0.03O4 nanotube, demonstrating the synergistic effect of co-catalysts for PEC water oxidation.
Project description:Hematite (?-Fe2O3) is one of the most promising candidates as a photoanode materials for solar water splitting. Owing to the difficulty in suppressing the significant charge recombination, however, the photoelectrochemical (PEC) conversion efficiency of hematite is still far below the theoretical limit. Here we report thick hematite films (?1500?nm) constructed by highly ordered and intimately attached hematite mesocrystals (MCs) for highly efficient PEC water oxidation. Due to the formation of abundant interfacial oxygen vacancies yielding a high carrier density of ?1020?cm-3 and the resulting extremely large proportion of depletion regions with short depletion widths (<10?nm) in hierarchical structures, charge separation and collection efficiencies could be markedly improved. Moreover, it was found that long-lived charges are generated via excitation by shorter wavelength light (below ?500?nm), thus enabling long-range hole transfer through the MC network to drive high efficiency of light-to-energy conversion under back illumination.
Project description:Photoelectrochemical (PEC) water splitting is a promising method for the conversion of solar energy into chemical energy stored in the form of hydrogen. Nanostructured hematite (?-Fe2 O3 ) is one of the most attractive materials for a highly efficient charge carrier generation and collection due to its large specific surface area and the short minority carrier diffusion length. In the present work, the PEC water splitting performance of nanostructured ?-Fe2 O3 is investigated which was prepared by anodization followed by annealing in a low oxygen ambient (0.03?% O2 in Ar). It was found that low oxygen annealing can activate a significant PEC response of ?-Fe2 O3 even at a low temperature of 400?°C and provide an excellent PEC performance compared with classic air annealing. The photocurrent of the ?-Fe2 O3 annealed in the low oxygen at 1.5?V vs. RHE results as 0.5?mA?cm-2 , being 20?times higher than that of annealing in air. The obtained results show that the ?-Fe2 O3 annealed in low oxygen contains beneficial defects and promotes the transport of holes; it can be attributed to the improvement of conductivity due to the introduction of suitable oxygen vacancies in the ?-Fe2 O3 . Additionally, we demonstrate the photocurrent of ?-Fe2 O3 annealed in low oxygen ambient can be further enhanced by Zn-Co LDH, which is a co-catalyst of oxygen evolution reaction. This indicates low oxygen annealing generates a promising method to obtain an excellent PEC water splitting performance from ?-Fe2 O3 photoanodes.
Project description:Hematite (?-Fe2O3) is a promising candidate for solar-to-hydrogen energy conversion. However, the low carrier mobility and extremely high charge recombination rate limit the practical application of hematite in solar water splitting. This paper describes the fabrication of a Fe2O3 photoanode with gradient incorporation of phosphorus (P) employing a facile dipping and annealing method to improve the charge separation for enhanced photoelectrochemical water oxidation. This gradient P incorporation increases the width of band bending over a large region in Fe2O3, which is crucial for promoting the charge separation efficiency in the bulk. Although both gradient and homogeneous P-incorporated Fe2O3 samples exhibit similar electrical conductivity, the Fe2O3 electrode with a gradient P concentration presents an additional charge separation effect. A photocurrent of ?1.48 mA cm-2 is obtained at 1.23 V vs. reversible hydrogen electrode (vs. RHE) under air mass 1.5G illumination. Additionally, the H2O oxidation kinetics of Fe2O3 with gradient P incorporation was further improved upon loading cobalt phosphate as cocatalyst, reaching a photocurrent of ?2.0 mA cm-2 at 1.23 V vs. RHE.
Project description:The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on ?-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on ?-Fe2O3 to formaldehyde with near unity Faradaic efficiency. A rate law analysis under quasi-steady-state conditions of PEC methanol oxidation indicates that rate of reaction is second order in the density of surface holes on hematite and independent of the applied potential. Analogous data on anatase TiO2 photoanodes indicate similar second-order kinetics for methanol oxidation with a second-order rate constant 2 orders of magnitude higher than that on ?-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on ?-Fe2O3 is retarded ?20-fold by H/D substitution. Employing these data, we propose a mechanism for methanol oxidation under 1 sun irradiation on these metal oxide surfaces and discuss the implications for the efficient PEC methanol oxidation to formaldehyde and concomitant hydrogen evolution.
Project description:The sun is the primary energy source of our planet and potentially can supply all societies with more than just their basic energy needs. Demand of electric energy can be satisfied with photovoltaics, however the global demand for fuels is even higher. The direct way to produce the solar fuel hydrogen is by water splitting in photoelectrochemical (PEC) cells, an artificial mimic of photosynthesis. There is currently strong resurging interest for solar fuels produced by PEC cells, but some fundamental technological problems need to be solved to make PEC water splitting an economic, competitive alternative. One of the problems is to provide a low cost, high performing water oxidizing and oxygen evolving photoanode in an environmentally benign setting. Hematite, ?-Fe2O3, satisfies many requirements for a good PEC photoanode, but its efficiency is insufficient in its pristine form. A promising strategy for enhancing photocurrent density takes advantage of photosynthetic proteins. In this paper we give an overview of how electrode surfaces in general and hematite photoanodes in particular can be functionalized with light harvesting proteins. Specifically, we demonstrate how low-cost biomaterials such as cyanobacterial phycocyanin and enzymatically produced melanin increase the overall performance of virtually no-cost metal oxide photoanodes in a PEC system. The implementation of biomaterials changes the overall nature of the photoanode assembly in a way that aggressive alkaline electrolytes such as concentrated KOH are not required anymore. Rather, a more environmentally benign and pH neutral electrolyte can be used.
Project description:As one of the most promising photoanode materials for photoelectrochemical (PEC) water oxidation, earth-abundant hematite has been severely restricted by its poor electrical conductivity, poor charge separation, and sluggish oxygen evolution reaction kinetics. FeO has an ability to produce hydrogen, while its preparation needs high temperature to reduce Fe3+ to Fe2+ by using H2 or CO gases. Here, Fe2O3- and FeO-based nanorods (NRs) on fluorine-doped tin oxide (FTO) substrate have been prepared, where the latter was obtained by doping Sn4+ ions in FeOOH to reduce Fe3+ ions to Fe2+. X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) measurements indicate that the dominant content of Fe element on the surface of Sn-doped Fe2O3 and Sn-FeOOH samples is Fe2+. FeO-based NRs have a Fe3O2/FeO heterostructure with some SnO2 nanoparticles distributed on their surface. These prepared samples were used as PEC photoanodes under a visible-light irradiation. The results showed that the modified FeO-based NRs have a photocurrent density of 0.2 mA cm-2 at 1.23 V vs reference hydrogen electrode (RHE) using Hg/HgO electrode as the reference electrode. Furthermore, they also have a better photocatalytic hydrogen evolution activity with a rate of 2.3 ?mol h-1 cm-1. The improved photocurrent and photocatalytic activity can be ascribed to the Sn-dopant, as the introduction of Sn4+ not only leads to the formation of the Fe3O2/FeO heterostructure but also increases the carrier concentration. Fe3O2/FeO heterostructure with SnO2 nanoparticles on its surface has a good band energy alignment, which is beneficial to the PEC water oxidation and reduction.
Project description:<h4>Objective</h4>Although photoelectrochemical (PEC) water splitting heralds the emergence of the hydrogen economy, the need for external bias and low efficiency stymies the widespread application of this technology. By coupling water splitting (in a PEC cell) to a microbial fuel cell (MFC) using <i>Escherichia coli</i> as the biocatalyst, this work aims to successfully demonstrate a sustainable hybrid PEC-MFC platform functioning solely by biocatalysis and solar energy, at zero bias. Through further chemical modification of the photo-anode (in the PEC cell) and biofilm (in the MFC), the performance of the hybrid system is expected to improve in terms of the photocurrent generated and hydrogen evolved.<h4>Methods</h4>The hybrid system constitutes the interconnected PEC cell with the MFC. Both PEC cell and MFC are typical two-chambered systems housing the anode and cathode. Au-TiO<sub>2</sub> hollow spheres and conjugated oligoelectrolytes were synthesised chemically and introduced to the PEC cell and MFC, respectively. Hydrogen evolution measurements were performed in triplicates.<h4>Results</h4>The hybrid PEC-MFC platform generated a photocurrent density of 0.35?mA/cm<sup>2</sup> (~70× enhancement) as compared with the stand-alone P25 standard PEC cell (0.005?mA/cm<sup>2</sup>) under one-sun illumination (100?mW/cm<sup>2</sup>) at zero bias (0?V vs. Pt). This increase in photocurrent density was accompanied by continuous H<sub>2</sub> production. No H<sub>2</sub> was observed in the P25 standard PEC cell whereas H<sub>2</sub> evolution rate was ~3.4??mol/h in the hybrid system. The remarkable performance is attributed to the chemical modification of <i>E. coli</i> through the incorporation of novel conjugated oligoelectrolytes in the MFC as well as the lower recombination rate and higher photoabsorption capabilities in the Au-TiO<sub>2</sub> hollow spheres electrode.<h4>Conclusions</h4>The combined strategy of photo-anode modification in PEC cells and chemically modified MFCs shows great promise for future exploitation of such synergistic effects between MFCs and semiconductor-based PEC water splitting.
Project description:One-dimensional heterostructure nanoarrays are efficiently promising as high performance electrodes for photo electrochemical (PEC) water splitting applications, wherein it is highly desirable for the electrode to have a broad light absorption, efficient charge separation and redox properties as well as defect free surface with high area suitable for fast interfacial charge transfer. We present highly active and unique photoelectrode for solar H2 production, consisting of silicon nanowires (SiNWs)/TiO2 core-shell structures. SiNWs are passivated to reduce defect sites and protected against oxidation in air or water by forming very thin carbon layer sandwiched between SiNW and TiO2 surfaces. This carbon layer decreases recombination rates and also enhances the interfacial charge transfer between the silicon and TiO2. A systematic investigation of the role of SiNW length and TiO2 thickness on photocurrent reveals enhanced photocurrent density up to 5.97 mA/cm(2) at 1.0 V vs.NHE by using C@SiNW/TiO2 nanoarrays with photo electrochemical efficiency of 1.17%.