Efficient photosynthesis of carbon monoxide from CO2 using perovskite photovoltaics

Artificial photosynthesis, mimicking nature in its efforts to store solar energy, has received considerable attention from the research community. Most of these attempts target the production of H2 as a fuel and our group recently demonstrated solar-to-hydrogen conversion at 12.3% efficiency. Here, in an effort to take this approach closer to real photosynthesis, which is based on the conversion of CO2, we demonstrate the efficient reduction of CO2 to carbon monoxide driven solely by simulated sunlight using water as the electron source. Employing series-connected perovskite photovoltaics and high-performance catalyst electrodes, we reach a solar-to-CO efficiency exceeding 6.5%, which represents a new benchmark in sunlight-driven CO2 conversion. Considering hydrogen as a secondary product, an efficiency exceeding 7% is observed. Furthermore, this study represents one of the first demonstrations of extended, stable operation of perovskite photovoltaics, whose large open-circuit voltage is shown to be particularly suited for this process

Solar energy conversion

If solar energy is to become a practical alternative to fossil fuels, we must have efficient ways to convert photons into electricity, fuel, and heat. The need for better conversion technologies is a driving force behind many recent developments in biology, materials, and especially nanoscience

Highly efficient planar perovskite solar cells through band alignment engineering

The simplification of perovskite solar cells (PSCs), by replacing the mesoporous electron selective layer (ESL) with a planar one, is advantageous for large-scale manufacturing. PSCs with a planar TiO2 ESL have been demonstrated, but these exhibit unstabilized power conversion efficiencies (PCEs). Herein we show that planar PSCs using TiO2 are inherently limited due to conduction band misalignment and demonstrate, with a variety of characterization techniques, for the first time that SnO2 achieves a barrier-free energetic configuration, obtaining almost hysteresis-free PCEs of over 18% with record high voltages of up to 1.19 V

Spontaneous crystal coalescence enables highly efficient perovskite solar cells

Perovskite solar cells have recently reached staggering efficiencies, through efforts focused on reducing grain boundaries, by enlarging the size of the crystalline domains that constitute the perovskite films. Here, we demonstrate that smaller crystallites within perovskite films spontaneously coalesce into larger ones, even when complete devices are stored in the dark at room temperature. We show that crystal coalescence greatly improves the performance of state of the art perovskite solar cells. Our results reveal the dynamic nature of the morphology of perovskite films and highlight the crucial role that coalescence plays in producing highly efficient device

In situ observation of picosecond polaron self-localisation in α-Fe2O3 photoelectrochemical cells

Hematite (α-Fe2O3) is the most studied artificial oxygen-evolving photo-anode and yet its efficiency limitations and their origin remain unknown. A sub-picosecond reorganisation of the hematite structure has been proposed as the mechanism which dictates carrier lifetimes, energetics and the ultimate conversion yields. However, the importance of this reorganisation for actual device performance is unclear. Here we report an in situ observation of charge carrier self-localisation in a hematite device, and demonstrate that this process affects recombination losses in photoelectrochemical cells. We apply an ultrafast, device-based optical-control method to resolve the subpicosecond formation of small polarons and estimate their reorganisation energy to be ~0.5 eV. Coherent oscillations in the photocurrent signals indicate that polaron formation may be coupled to specific phonon modes (<100 cm-1). Our results bring together spectroscopic and device characterisation approaches to reveal new photophysics of broadly-studied hematite devices

Impact of monovalent cation halide additives on the structural and optoelectronic properties of CH<inf>3</inf>NH<inf>3</inf>PbI<inf>3</inf> perovskite

The influence of monovalent cation halide additives on the optical, excitonic, and electrical properties of CH$_{3}$NH$_{3}$PbI$_{3}$ perovskite is reported. Monovalent cation halide with similar ionic radii to Pb$^{2+}$, including Cu$^{+}$, Na$^{+}$, and Ag$^{+}$, have been added to explore the possibility of doping. Significant reduction of sub-bandgap optical absorption and lower energetic disorder along with a shift in the Fermi level of the perovskite in the presence of these cations has been observed. The bulk hole mobility of the additive-based perovskites as estimated using the space charge limited current method exhibits an increase of up to an order of magnitude compared to the pristine perovskites with a significant decrease in the activation energy. Consequentially, enhancement in the photovoltaic parameters of additive-based solar cells is achieved. An increase in open circuit voltage for AgI (≈1.02 vs 0.95 V for the pristine) and photocurrent density for NaI- and CuBr-based solar cells (≈23 vs 21 mA cm$^{−2}$ for the pristine) has been observed. This enhanced photovoltaic performance can be attributed to the formation of uniform and continuous perovskite film, better conversion, and loading of perovskite, as well as the enhancement in the bulk charge transport along with a minimization of disorder, pointing towards possible surface passivation.M.A.J. thanks Nyak Technology Limited for a PhD scholarship. M.I.D., S.M.Z., and M.G. thank the King Abdulaziz City for Science and Technology (KACST) and Swiss National Science Foundation (SNSF) for financial support. N.A. gratefully acknowledges financial support from the Swiss confederation under Swiss Government Scholarship program. The authors would like to thank Dr. Pierre Mettraux in Molecular and Hybrid Materials Characterization Center, EPFL for carrying out XPS measurements. A.S. gratefully acknowledges financial support from the Indo-UK APEX project. S.P.S. acknowledges Royal Scociety London for the Newton Fellowship. R.H.F, M.A.J., and A.S. would like to acknowledge the support from EPSRC.This is the author accepted manuscript. The final version is available from Wiley via http://dx.doi.org/10.1002/aenm.20150247

Kinetics of photoelectrochemical oxidation of methanol on hematite photoanodes

The kinetics of photoelectrochemical (PEC) oxidation of methanol, as a model organic substrate, on α-Fe2O3 photoanodes are studied using photoinduced absorption spectroscopy and transient photocurrent measurements. Methanol is oxidized on α-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 α-Fe2O3. Kinetic isotope effect studies determine that the rate constant for methanol oxidation on α-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

A perspective on using experiment and theory to identify design principles in dye-sensitized solar cells

Dye-sensitized solar cells (DSCs) have been the subject of wide-ranging studies for many years because of their potential for large-scale manufacturing using roll-to-roll processing allied to their use of earth abundant raw materials. Two main challenges exist for DSC devices to achieve this goal; uplifting device efficiency from the 12 to 14% currently achieved for laboratory-scale ‘hero’ cells and replacement of the widely-used liquid electrolytes which can limit device lifetimes. To increase device efficiency requires optimized dye injection and regeneration, most likely from multiple dyes while replacement of liquid electrolytes requires solid charge transporters (most likely hole transport materials – HTMs). While theoretical and experimental work have both been widely applied to different aspects of DSC research, these approaches are most effective when working in tandem. In this context, this perspective paper considers the key parameters which influence electron transfer processes in DSC devices using one or more dye molecules and how modelling and experimental approaches can work together to optimize electron injection and dye regeneration. This paper provides a perspective that theory and experiment are best used in tandem to study DSC device

Stability and Electronic Properties of TiO2 Nanostructures With and Without B and N Doping

We address one of the main challenges to TiO2-photocatalysis, namely band gap narrowing, by combining nanostructural changes with doping. With this aim we compare TiO2's electronic properties for small 0D clusters, 1D nanorods and nanotubes, 2D layers, and 3D surface and bulk phases using different approximations within density functional theory and GW calculations. In particular, we propose very small (R < 0.5 nm) but surprisingly stable nanotubes with promising properties. The nanotubes are initially formed from TiO2 layers with the PtO2 structure, with the smallest (2,2) nanotube relaxing to a rutile nanorod structure. We find that quantum confinement effects - as expected - generally lead to a widening of the energy gap. However, substitutional doping with boron or nitrogen is found to give rise to (meta-)stable structures and the introduction of dopant and mid-gap states which effectively reduce the band gap. Boron is seen to always give rise to n-type doping while depending on the local bonding geometry, nitrogen may give rise to n-type or p-type doping. For under coordinated TiO2 surface structures found in clusters, nanorods, nanotubes, layers and surfaces nitrogen gives rise to acceptor states while for larger clusters and bulk structures donor states are introduced