Considerations for the Accurate Measurement of Incident Photon to Current Efficiency in Photoelectrochemical Cells

In this paper we review some of the considerations and potential sources of error when conducting Incident Photon to Current Efficiency (IPCE) measurements, with focus on photoelectrochemical (PEC) cells for water splitting. The PEC aspect introduces challenges for accurate measurements often not encountered in dry PV cells. These can include slow charge transfer dynamics and, depending on conditions (such as a white light bias, which is important for samples with non-linear response to light intensity), possible composition changes, mostly at the surface, that a sample may gradually undergo as a result of chemical interactions with the aqueous electrolyte. These can introduce often-overlooked dependencies related to the timing of the measurement, such as a slower measurement requirement in the case of slow charge transfer dynamics, to accurately capture the steady-state response of the system. Fluctuations of the probe beam can be particularly acute when a Xe lamp with monochromator is used, and longer scanning times also allow for appreciable changes in the sample environment, especially when the sample is under realistically strong white light bias. The IPCE measurement system and procedure need to be capable of providing accurate measurements under specific conditions, according to sample and operating requirements. To illustrate these issues, complications, and solution options, we present example measurements of hematite photoanodes, leading to the use of a motorized rotating mirror stage to solve the inherent fluctuation and drift-related problems. For an example of potential pitfalls in IPCE measurements of metastable samples, we present measurements of BiVO4 photoanodes, which had changing IPCE spectral shapes under white-light bias.

Fabrication of Semi-Transparent SrTaO2N Photoanodes with a GaN Underlayer Grown via Atomic Layer Deposition

Quaternary metal oxynitride-based photoanodes with a large light transmittance are promising for high solar-to-hydrogen (STH) conversion efficiency in photoelectrochemical (PEC) tandem cells. Transparent substrates to support PEC water-splitting were fabricated using atomic layer deposition (ALD) to synthesize 30 and 60 nm GaN on SiC sub-strates. A generalized approach was used to grow a quaternary metal oxynitride, i.e. SrTaO2N thin film on the GaN/SiC substrates. The transparency above 60% in the wide solar spectrum highlights its availability of transmit-ting visible light to the rear side. A photocurrent onset at ca. −0.4 V vs. reversible hydrogen electrode (RHE) was achieved by the SrTaO2N/GaN/SiC photoanodes in a 0.1 M NaOH electrolyte under simulated solar irradiation. This paves the way for construction of hierarchically nanostructured tandem PEC cells. This work demonstrates the viabil-ity of integrating ALD in constructing substrates for semi-transparent quaternary metal oxynitride photoanodes.

Electrodeposition of cuprous oxide on a porous copper framework for an improved photoelectrochemical performance

Photoelectrochemical (PEC) water splitting can be an efficient and economically feasible alternative for hydrogen production if easily processed photoelectrodes made of inexpensive and abundant materials are employed. Here, we present the preparation of porous Cu2O photocathodes with good PEC performance using solely inexpensive electrodeposition methods. Firstly, porous Cu structures with delicate pore networks were deposited on flat Cu substrates employing hydrogen-bubble-assisted Cu deposition. In a second electrodeposition step, the porous Cu structures were mechanically reinforced and subsequently detached from the substrates to obtain free-standing porous frameworks. In a third and final step, photoactive Cu2O films were electrodeposited. The PEC water splitting performance in 0.5 M Na2SO4 (pH ∼6) shows that these photocathodes have photocurrents of up to −2.25 mA cm−2 at 0 V versus RHE while maintaining a low dark current. In contrast, the Cu2O deposited on a flat Cu sample showed photocurrents only up to −1.25 mA cm−2. This performance increase results from the significantly higher reactive surface area while maintaining a thin and homogeneous Cu2O layer with small grain sizes and therefore higher hole concentrations as determined by Mott-Schottky analysis. The free-standing porous Cu2O samples show a direct optical transmittance of 23% (λ = 400–800 nm) and can therefore be used in tandem structures with a photoanode in full PEC cells. Graphical abstract

CVD grown GaSbxN1-x films as visible-light active photoanodes

The III-V semiconductor GaN is a promising material for photoelectrochemical (PEC) cells, however the large bandgap of 3.45 eV is a considerable hindrance for the absorption of visible light. Therefore,...

A semitransparent particulate photoanode composed of SrTiO3 powder anchored on titania nanosheets

The development of semitransparent photoanodes is necessary to permit the construction of tandem-type photoelectrochemical (PEC) cells for water splitting in conjunction with an appropriate photocathode as the bottom cell. The...

Fabrication of Bilayer Fe2O3/ZnO Photoanode and its Photoelectrochemical Performance

Hematite (Fe2O3) is one of the abundant magnetic materials in nature. Hematite has good absorption ability in the region visible light and good electrochemical stability, which make this material is potential as photoanode for photoelectrochemical (PEC) cells. However, Fe2O3 has some disadvantages such as short hole diffusion length and low hole mobility. Therfore, it is necessarily to combine Fe2O3 with photocatalyst material to improve photoelectrochemical performances. ZnO is ones of photocatalist material with good electron mobility, wide band gaps, cheap and are easily fabricated. The aim of this study is to investigate the performance of bilayer Fe2O3/ZnO as photoanode for photoelectrochemical cell. The bilayer Fe2O3/ZnO was prepared by spin-coating techniques and doctor blade methods. The samples were characterized by X-ray diffarction, and Scanning Electron Microscopy. The performance of photoelectrochemical cell was investigated by Cyclic Voltammetry (CV) under light illumination. The result indicate that bilayer Fe2O3/ZnO has good photoelectrochemical properties.

Inhibition of Photoconversion Activity in Self-Assembled ZnO-Graphene Quantum Dots Aggregated by 4-Aminophenol Used as a Linker

The aggregation of zinc oxide nanoparticles leads to an increased absorbance in the ultraviolet-visible region by an induced light scattering effect. Herein, we demonstrate the inhibition of photoconversion activity in ZnO-graphene core-shell quantum dots (QD) (ZGQDs) agglomerated by 4-aminophenol (4-AP) used as a linker. The ZnO-graphene quantum dots (QD) aggregates (ZGAs) were synthesized using a facile solvothermal process. The ZGAs revealed an increased absorbance in the wavelengths between 350 and 750 nm as compared with the ZGQDs. Against expectation, the calculated average photoluminescence lifetime of ZGAs was 7.37 ns, which was 4.65 ns longer than that of ZGQDs and was mainly due to the high contribution of a slow (τ2, τ3) component by trapped carriers in the functional groups of graphene shells and 4-AP. The photoelectrochemical (PEC) cells and photodetectors (PDs) were fabricated to investigate the influence of ZGAs on the photoconversion activity. The photocurrent density of PEC cells with ZGAs was obtained as 0.04 mA/cm2 at 0.6 V, which was approximately 3.25 times lower than that of the ZGQDs. The rate constant value of the photodegradation value of rhodamine B was also decreased by around 1.4 times. Furthermore, the photoresponsivity of the PDs with ZGAs (1.54 μA·mW−1) was about 2.5 times as low as that of the PDs with ZGQDs (3.85 μA·mW−1). Consequently, it suggests that the device performances could be degraded by the inhibition phenomenon of the photoconversion activity in the ZGAs due to an increase of trap sites.

Synergies of co-doping in ultra-thin hematite photoanodes for solar water oxidation: In and Ti as representative case

Solar energy induced water splitting in photoelectrochemical (PEC) cells is one of the most sustainable ways of hydrogen production. In this work, hematite (α-Fe2O3) thin film were modified by In3+ and Ti4+ co-doping for enhanced PEC performance.

Recent developments in carbon nitride based films for photoelectrochemical water splitting

As an emerging semiconductor for PEC cells, metal-free g-CN has generally attracted research attention from the community due to its merits, namely an appropriate bandgap, abundant composition elements, good thermal stability and non-toxicity.

A solar-responsive zinc oxide photoanode for solar-photon-harvester photoelectrochemical (PEC) cells

Deposition of highly efficient, nanostructured, solar-responsive ZnO (SRZO) photoanode for H2 generation by solution precursor plasma spray deposition technique. In PEC Cell, SRZO shows a STH conversion efficiency of 2.32% as seen by evolved H2.