Co doping and oxygen vacancies induced spin polarization and full-space electric field in ZnSn(OH)6 for boosting photocatalytic CO2 reduction via accelerating directional carriers separation

Horizontal transmission of the polar electric field to the equator

The built-in electric field generated by polar materials is one of the most effective strategies to promote the separation of photogenerated electron-hole pairs in the field of photocatalysis. However, because of the complexity and diversity of the built-in electric field in polar materials, it is not clear how to enhance the photocatalytic performance and how to control the polar electric field effectively. To this end, four-layered bismuth oxyhalides, BiOX, and BiOXO3 (X = Br, I) were synthesized by a simple hydrothermal method. X-ray diffraction, Fourier transform infrared spectroscopy, and X-ray photoelectron spectroscopy analysis confirmed that they all have the structure characteristics of a sillenite phase. Scanning electron microscopy images show that they all have the morphology of nanosheets. Among them, BiOBrO3 was successfully synthesized and characterized for the first time in the present work. The order of photocatalytic performance (including carrier's lifetime, photocurrent density, and H2 evolution rate) of the four compounds is listed as follows: BiOBrO3 > BiOI > BiOIO3 > BiOBr. In the bulk of the BiOXO3 photocatalyst, the spontaneous polar built-in electric field along the [001] direction is the crucial factor to inhibit the recombination of photogenerated electron-hole pairs, while the surface polar electric field in BiOI can outstandingly inhibit the recombination of photogenerated electron-hole pairs due to the breaking of the mirror symmetry. Therefore, regulating the microstructure and composition of the structure unit, which generates the built-in electric field, can indeed control the magnitude, direction, and effects of built-in electric fields. In practice, we should carefully adjust the strategy according to the actual situation so as to reasonably design and use the polar electric field, giving full play to its role and enhancing the photocatalytic performance.

Interplanetary electric field coupling with the magnetosphere has been analyzed predominantly using data from the Wind magnetometer and the Polar electric field instrument. The coupling was investigated using the Polar Electric Field Instrument (EFI) to measure the electric field in the northern polar cap immediately following sharp southward turnings of the IMF as observed by Wind. Southward turnings were chosen which exhibited a sudden change of the IMF north–south component from BZ > 0 to BZ < 0 (GSM coordinates) after an hour or more of relatively stable conditions, and for which Polar was in the northern polar cap. These BZ changes correspond to EY changes in the interplanetary electric field. For each of the 30 identified events, a time was estimated for the arrival of the IMF change at the magnetopause using the solar wind speed observed by the Wind Solar Wind Experiment (SWE), and Polar electric field data were examined to identify responses. For many of the selected events (about one third), abrupt changes of state in the magnetospheric electric field were evident with timing that matched the expected solar wind arrival time at Earth. For events for which additional data were available, we conducted in‐depth examination of the individual events using IMP 8, Geotail, and GOES 9. In one such event, GOES 9 data showed a substorm growth phase and onset which also corresponded to features in the solar wind observed by Wind, Geotail, and IMP 8. In addition to the individual event studies, a superposed epoch analysis of all available events revealed a consistent rise in the mean polar cap electric field about 15 min following sharp IMF southward turnings.

Using realistic models of the ionospheric conductivity and the field‐aligned currents, we have determined how the distribution of the electric field in the polar cap ionosphere is controlled by the day‐night contrast in conductivity and by the relative strengths of the region 1 and region 2 field‐aligned currents. The sunward directed conductivity gradient acts to set up a space charge in the polar cap which crowds the equipotentials toward the dawn sector for current sources of both region 1 and region 2 polarity; this effectively shifts the polar cap convection pattern toward dawn. Our results show further that for a given conductivity distribution the orientation of the electric field in the central polar cap depends sensitively on the relative strengths of the Birkeland current pairs: for very weak region 2 currents (quiet times) the polar electric field is directed ≈ 60° east of noon, for equal region 1 and 2 currents (disturbed times) the direction is ≈ 10° east of noon, and for stronger region 2 than 1 currents (which may happen on occasion) the electric field points into the prenoon sector. These findings imply that the orientation of the polar cap electric field should serve as a measure or index of the ratio of region 1 to region 2 net current intensity and should possess correlations with geomagnetic activity similar to those of this ratio. This analysis does not include effects of possible source currents in the region of the polar cusp.

Increase of the Kosterlitz-Thouless critical temperature by the external electric field

Increase of the Kosterlitz-Thouless critical temperature by the external electric field

Solar Photocatalysis

Tungsten and oxygen dual vacancies regulation of the S-scheme ZnSe/ZnWO4 heterojunction with local polarization electric field for efficient CO2 photocatalytic reduction

Cadmium sulfide (CdS) is a photocatalyst widely used for efficient H2 production under visible light irradiation, due to its narrow bandgap and suitable conduction band position. However, the fast recombination of carriers results in their low utilization. In order to improve photocatalytic hydrogen production, it reports the successful introduction of metallic Cd and S vacancies on CdS nanorods (CdS NRs) by a facile in situ chemical reduction method, using a thermal treatment process. This procedure generates interfacial and polarization electric fields, that significantly improve the photocatalytic hydrogen production performance of CdS NRs in sodium sulfide and sodium sulfite aqueous solutions, under visible light irradiation (λ>420nm). The introduction of these electric fields is believed to improve charge separation and facilitate faster interfacial charge migration, resulting in a significantly optimized catalyst, with a photocatalytic hydrogen evolution rate of up to 10.6mmol-1 g-1 h-1 with apparent quantum efficiency (AQE) of 12.1% (420nm), which is 8.5 times higher than that of CdS. This work provides a useful method to introduce metallic and S vacancies on metal sulfide photocatalysts to build local polarization and interfacial electric fields for high-performance photocatalytic H2 production.

Plasmonic Ag nanoparticles decorated SrTiO3 nanocubes for enhanced photocatalytic CO2 reduction and H2 evolution under visible light irradiation

A significant amount of carbon dioxide is released into the atmosphere as a result of the extensive usage of fossil fuels. The photocatalytic reduction and conversion of CO2 under visible light into alternative renewable solar fuels or other oxygenated products (methane, formaldehyde, methanol, and formic acid) are practical and efficient methods for reducing atmospheric carbon pollution. Functional materials containing titanium dioxide (TiO2) have attracted significant interest for the photocatalytic reduction of CO2. In this direction, many studies have been conducted in recent years, especially on solar energy harvesting and the charge separation, adsorption, activation, and reduction of CO2 on enhanced TiO2. Recent studies have shown that brookite TiO2 (BT) was the most active photocatalyst, followed by rutile and anatase. Therefore, this study aims to review in detail the recent advances in the development of selective and active catalysts for photocatalytic CO2 reduction using titanium dioxide with a brookite structure. This review evaluates the most common methods for obtaining BT. It discusses various engineered strategies, including doping with metallic or non-metallic heteroatoms, addition of a co-catalyst, formation of heterojunctions, and other algorithms to improve the CO2 reduction mechanism. The influence of another phase and crystal facets on the photocatalytic CO2 reduction reaction are discussed in detail. The problems associated with BT-based photocatalysts, namely, their modest visible-light absorption, slow interfacial charge separation, and poor surface catalytic dynamics, are further discussed, along with possible solutions. To stimulate additional research in this field, the difficulties and potential advantages of photocatalytic CO2 conversion methods are discussed.

The conversion of CO2 to valuable substances (methane, methanol, formic acid, etc.) by photocatalytic reduction has important significance for both the sustainable energy supply and clean environment technologies. This review systematically summarized recent progress in this field and pointed out the current challenges of photocatalytic CO2 reduction while using metal-organic frameworks (MOFs)-based materials. Firstly, we described the unique advantages of MOFs based materials for photocatalytic reduction of CO2 and its capacity to solve the existing problems. Subsequently, the latest research progress in photocatalytic CO2 reduction has been documented in detail. The catalytic reaction process, conversion efficiency, as well as the product selectivity of photocatalytic CO2 reduction while using MOFs based materials are thoroughly discussed. Specifically, in this review paper, we provide the catalytic mechanism of CO2 reduction with the aid of electronic structure investigations. Finally, the future development trend and prospect of photocatalytic CO2 reduction are anticipated.

Efficient transfer of charge carriers through a fast transport pathway is crucial to excellent photocatalytic reduction performance in solar-driven CO2 reduction, but it is still challenging to effectively modulate the electronic transport pathway between photoactive motifs by feasible chemical means. In this work, we propose a thermally induced strategy to precisely modulate the fast electron transport pathway formed between the photoactive motifs of a porphyrin metal-organic framework using thorium ion with large ionic radius and high coordination number as the coordination-labile metal node. As a result, the stacking pattern of porphyrin molecules in the framework before and after the crystal transformations has changed dramatically, which leads to significant differences in the separation efficiency of photogenerated carriers in MOFs. The rate of photocatalytic reduction of CO2 to CO by IHEP-22(Co) reaches 350.9 μmol·h-1·g-1, which is 3.60 times that of IHEP-21(Co) and 1.46 times that of IHEP-23(Co). Photoelectrochemical characterizations and theoretical calculations suggest that the electron transport channels formed between porphyrin molecules inhibit the recombination of photogenerated carriers, resulting in high performance for photocatalytic CO2 reduction. The interaction mechanism of CO2 with IHEP-22(Co) was clarified by using in-situ electron paramagnetic resonance, in-situ diffuse reflectance infrared Fourier transform spectroscopy, in-situ extended X-ray absorption fine structure spectroscopy, and theoretical calculations. These results provide a new method to regulate the efficient separation and migration of charge carriers in CO2 reduction photocatalysts and will be helpful to guide the design and synthesis of photocatalysts with superior performance for the production of solar fuels.

Advances and roles of oxygen vacancies in semiconductor photocatalysts for solar-driven CO2 reduction

Photocatalytic CO2 reduction over g-C3N4 based heterostructures: Recent progress and prospects