Photosynthesis is nature's route to convert intermittent solar irradiation into storable energy, while its use for an industrial energy supply is impaired by low efficiency. Artificial photosynthesis ...provides a promising alternative for efficient robust carbon-neutral renewable energy generation. The approach of direct hydrogen generation by photoelectrochemical water splitting utilizes customized tandem absorber structures to mimic the Z-scheme of natural photosynthesis. Here a combined chemical surface transformation of a tandem structure and catalyst deposition at ambient temperature yields photocurrents approaching the theoretical limit of the absorber and results in a solar-to-hydrogen efficiency of 14%. The potentiostatically assisted photoelectrode efficiency is 17%. Present benchmarks for integrated systems are clearly exceeded. Details of the in situ interface transformation, the electronic improvement and chemical passivation are presented. The surface functionalization procedure is widely applicable and can be precisely controlled, allowing further developments of high-efficiency robust hydrogen generators.
We unravel for the first time the origin of the poor carrier transport properties of BiVO4, a promising metal oxide photoanode for solar water splitting. Time-resolved microwave conductivity (TRMC) ...measurements reveal an (extrapolated) carrier mobility of ∼4 × 10–2 cm2 V–1 s–1 for undoped BiVO4 under ∼1 sun illumination conditions, which is unusually low for a photoanode material. The poor carrier mobility is compensated by an unexpectedly long carrier lifetime of 40 ns. This translates to a relatively long diffusion length of 70 nm, consistent with the high quantum efficiencies reported for BiVO4 photoanodes. Tungsten (W) doping is found to strongly decrease the carrier mobility by introducing intermediate-depth donor defects as carrier traps. At the same time, the increased carrier density improves the overall photoresponse, which confirms that bulk electronic conductivity is one of the main performance bottlenecks for BiVO4.
The remaining carbon budgets compatible with limiting global warming to 1.5 or 2 °C above preindustrial levels are shrinking rapidly. An already firmly anticipated, but highly controversial measure ...to mitigate this challenge is the large‐scale implementation of negative emissions, removing carbon dioxide from the atmosphere. Many of the currently considered negative emission technologies (NET) are based on natural photosynthesis, associated with large land footprints. Photoelectrochemical carbon sinks, on the other hand, promise to combine high conversion efficiencies with versatile storage options. Efficient sink products differ from the products typically considered for solar fuels, which will require novel catalysts and device designs. The development of efficient devices also has to take into account climatic parameters of the local environment as especially the ambient temperature affects device operation. While still in an early stage of development, carbon drawdown by such an artificial photosynthesis approach could be a valuable extension of the portfolio of NET.
Negative CO2 emission technologies will be required to limit global warming. Photoelectrochemical approaches, converting CO2 to a sink product for safe and facile long‐term storage, are a hitherto barely explored approach to this end. In contrast to solar fuel production, energy storage is not desirable and hydrocarbons should be avoided to realize high conversion efficiencies.
Efficient unassisted solar water splitting, a pathway to storable renewable energy in the form of chemical bonds, requires optimization of a photoelectrochemical device based on photovoltaic tandem ...heterojunctions. We report a monolithic photocathode device architecture that exhibits significantly reduced surface reflectivity, minimizing parasitic light absorption and reflection losses. A tailored multifunctional crystalline titania interphase layer acts as a corrosion protection layer, with favorable band alignment between the semiconductor conduction band and the energy level for water reduction, facilitating electron transport at the cathode–electrolyte interface. It also provides a favorable substrate for adhesion of high-activity Rh catalyst nanoparticles. Under simulated AM 1.5G irradiation, solar-to-hydrogen efficiencies of 19.3 and 18.5% are obtained in acidic and neutral electrolytes, respectively. The system reaches a value of 0.85 of the theoretical limit for photoelectrochemical water splitting for the energy gap combination employed in the tandem-junction photoelectrode structure.
Radiation exposure occurs in X-ray guided interventional procedures or computed tomography (CT) and γ-H2AX-foci are recognized to represent DNA double-strand breaks (DSBs) as a biomarker for ...radiation induced damage. Antioxidants may reduce the induction of γ-H2AX-foci by binding free radicals. The aim of this study was to establish a dose-effect relationship and a time-effect relationship for the individual antioxidants on DSBs in human blood lymphocytes.
Blood samples from volunteers were irradiated with 10 mGy before and after pre-incubation with different antioxidants (zinc, trolox, lipoic acid, ß-carotene, selenium, vitamin E, vitamin C, N-acetyl-L-cysteine (NAC) and Q 10). Thereby, different pre-incubation times, concentrations and combinations of drugs were evaluated. For assessment of DSBs, lymphocytes were stained against the phosphorylated histone variant γ-H2AX.
For zinc, trolox and lipoic acid regardless of concentration or pre-incubation time, no significant decrease of γ-H2AX-foci was found. However, ß-carotene (15%), selenium (14%), vitamin E (12%), vitamin C (25%), NAC (43%) and Q 10 (18%) led to a significant reduction of γ-H2AX-foci at a pre-incubation time of 1 hour. The combination of different antioxidants did not have an additive effect.
Antioxidants administered prior to irradiation demonstrated the potential to reduce γ-H2AX-foci in blood lymphocytes.
The contact of water with semiconductors typically changes its surface electronic structure by oxidation or corrosion processes. A detailed knowledge-or even control of-the surface structure is ...highly desirable, as it impacts the performance of opto-electronic devices from gas-sensing to energy conversion applications. It is also a prerequisite for density functional theory-based modelling of the electronic structure in contact with an electrolyte. The P-rich GaP(100) surface is extraordinary with respect to its contact with gas-phase water, as it undergoes a surface reordering, but does not oxidise. We investigate the underlying changes of the surface in contact with water by means of theoretically derived reflection anisotropy spectroscopy (RAS). A comparison of our results with experiment reveals that a water-induced hydrogen-rich phase on the surface is compatible with the boundary conditions from experiment, reproducing the optical spectra. We discuss potential reaction paths that comprise a water-enhanced hydrogen mobility on the surface. Our results also show that computational RAS-required for the interpretation of experimental signatures-is feasible for GaP in contact with water double layers. Here, RAS is sensitive to surface electric fields, which are an important ingredient of the Helmholtz-layer. This paves the way for future investigations of RAS at the semiconductor-electrolyte interface.
Indium phosphide and derived compound semiconductors are materials often involved in high-efficiency solar water splitting due to their versatile opto-electronic properties. Surface corrosion, ...however, typically deteriorates the performance of photoelectrochemical solar cells based on this material class. It has been reported that (photo)electrochemical surface functionalisation protects the surface by combining etching and controlled corrosion. Nevertheless, the overall involved process is not fully understood. Therefore, access to the electrochemical interface structure under operando conditions is crucial for a more detailed understanding. One approach for gaining structural insight is the use of operando reflection anisotropy spectroscopy. This technique allows the time-resolved investigation of the interfacial structure while applying potentials in the electrolyte. In this study, p-doped InP(100) surfaces are cycled between anodic and cathodic potentials in two different electrolytes, hydrochloric acid and sulphuric acid. For low, 10 mM electrolyte concentrations, we observe a reversible processes related to the reduction of a surface oxide phase in the cathodic potential range which is reformed near open-circuit potentials. Higher concentrations of 0.5 N, however, already lead to initial surface corrosion.
The aim of this study was to evaluate the accuracy of modern low-field magnetic resonance imaging (MRI) for lung nodule detection and to correlate nodule size measurement with computed tomography ...(CT) as reference.
Between November 2020 and July 2021, a prospective clinical trial using low-field MRI at 0.55 T was performed in patients with known pulmonary nodules from a single academic medical center. Every patient underwent MRI and CT imaging on the same day. The primary aim was to evaluate the detection accuracy of pulmonary nodules using MRI with transversal periodically rotated overlapping parallel lines with enhanced reconstruction in combination with coronal half-Fourier acquired single-shot turbo spin-echo MRI sequences. The secondary outcome was the correlation of the mean lung nodule diameter with CT as reference according to the Lung Imaging Reporting and Data System. Nonparametric Mann-Whitney U test, Spearman rank correlation coefficient, and Bland-Altman analysis were applied to analyze the results.
A total of 46 participants (mean age ± SD, 66 ± 11 years; 26 women) were included. In a blinded analysis of 964 lung nodules, the detection accuracy was 100% for those ≥6 mm (126/126), 80% (159/200) for those ≥4-<6 mm, and 23% (147/638) for those <4 mm in MRI compared with reference CT. Spearman correlation coefficient of MRI and CT size measurement was r = 0.87 ( P < 0.001), and the mean difference was 0.16 ± 0.9 mm.
Modern low-field MRI shows excellent accuracy in lesion detection for lung nodules ≥6 mm and a very strong correlation with CT imaging for size measurement, but could not compete with CT in the detection of small nodules.