A direct coupled electrochemical system for capture and conversion of CO2 from oceanwater.

Capture and conversion of CO2 from oceanwater can lead to net-negative emissions and can provide carbon source for synthetic fuels and chemical feedstocks at the gigaton per year scale. Here, we report a direct coupled, proof-of-concept electrochemical system that uses a bipolar membrane electrodialysis (BPMED) cell and a vapor-fed CO2 reduction (CO2R) cell to capture and convert CO2 from oceanwater. The BPMED cell replaces the commonly used water-splitting reaction with one-electron, reversible redox couples at the electrodes and demonstrates the ability to capture CO2 at an electrochemical energy consumption of 155.4 kJ mol-1 or 0.98 kWh kg-1 of CO2 and a CO2 capture efficiency of 71%. The direct coupled, vapor-fed CO2R cell yields a total Faradaic efficiency of up to 95% for electrochemical CO2 reduction to CO. The proof-of-concept system provides a unique technological pathway for CO2 capture and conversion from oceanwater with only electrochemical processes.

Patterned nanofiber air filters with high optical transparency, robust mechanical strength, and effective PM2.5 capture capability.

PM2.5, due to its small particle size, strong activity, ease of the attachment of toxic substances and long residence time in the atmosphere, has a great impact on human health and daily production. In this work, we have presented patterned nanofiber air filters with high optical transparency, robust mechanical strength and effective PM2.5 capture capability. Here, to fabricate a transparency air filter by a facile electrospinning method, we chose three kinds of patterned wire meshes with micro-structures as negative receiver substrates and directly electrospun polymer fibers onto the supporting meshes. Compared with randomly oriented nanofibers (named "RO NFs" in this paper) and commercially available facemasks, the patterned air filters showed great mechanical properties, and the water contact angles on their surfaces were about 122-143° (the water contact angle for RO NFs was 81°). In addition, the patterned nanofibers exhibited high porosity (>80%), and their mean pore size was about 0.5838-0.8686 µm (the mean pore size of RO NFs was 0.4374 µm). The results indicate that the transparent patterned air filters have the best PM2.5 filtration efficiency of 99.99% at a high transmittance of ∼69% under simulated haze pollution.

Involvement of hypoxia-inducible factor-1 alpha in the upregulation of P-glycoprotein in refractory epilepsy.

To explore the involvement of hypoxia-inducible factor-1 alpha (HIF-1α) in the upregulation of P-glycoprotein (P-gp) in refractory epilepsy. Brain tissue specimens were collected and analyzed for expression of HIF-1α and P-gp using an immunohistochemical (IHC) staining method in both refractory epilepsy group and control group. Correlation between HIF-1α and P-gp expression level in refractory epilepsy group was analyzed. Then, a hypoxia cell model was established by simulating the nerve cell hypoxic microenvironment in the human U251 cell line using cobalt chloride (CoCl2). Western blot analysis was used to detect expression levels of HIF-1α and P-gp in the hypoxic cell model. Finally, expression of HIF-1α and P-gp was detected using real-time quantitative PCR and Western blot, respectively, after U251 hypoxic model cells were infected with HIF-1α siRNA. IHC scores of HIF-1α and P-gp in refractory epilepsy group were significantly higher than that in control group. In addition, the expression of HIF-1α was positively correlated with the expression of P-gp in refractory epilepsy group. Expression levels of HIF-1α and P-gp in U251 cells cultured with 250 µmol/L CoCl2 for 48 hours were significantly higher than that in controls. After transfection with siRNA targeting HIF-1α, expressions of HIF-1α and P-gp at mRNA and protein level were decreased, respectively, in the hypoxia cell model. HIF-1α may be involved in the upregulation of P-gp in refractory epilepsy through inducement of P-gp expression. Therefore, activation of the HIF-1α/P-gp pathway is one hypothesis proposed to explain the pathogenesis of refractory epilepsy.

A novel preparation method for ZnO/γ-Al2O3 nanofibers with enhanced absorbability and improved photocatalytic water-treatment performance by Ag nanoparticles.

A novel method for synthesizing ZnO/γ-Al2O3 nanofibers by electrospinning and subsequent calcination is reported. The prepared nanofibers were characterized by scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy-dispersive X-ray spectroscopy (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). The ZnO/γ-Al2O3 nanofibers exhibited excellent capacity for adsorbing organics with a negative zeta potential such as methyl orange (95.8%) and heavy metal ions such as Cr(vi) in aqueous solution. The mechanism of adsorption was investigated, and the adsorption results were fitted using the Langmuir and Freundlich models. Once silver nanoparticles (Ag NPs) were decorated on the surface of the nanofibers by photoreduction, the Ag/ZnO/γ-Al2O3 nanofibers manifested efficient photocatalytic degradation of methyl orange under UV-light illumination. Results confirmed that our Ag/ZnO/γ-Al2O3 nanofibers are a promising adsorbent for the removal of methyl orange and Cr(vi) ions and the adsorbent can be sustainably reused.

Reliable Performance Characterization of Mediated Photocatalytic Water-Splitting Half Reactions.

Photocatalytic approaches using two sets of semiconductor particles and a pair of redox-shuttle mediators are considered as a safe and economic solution for solar water splitting. Here, accurate experimental characterization techniques for photocatalytic half reactions are reported, investigating the gas as well as the liquid products. The methods are exemplified utilizing photocatalytic titania particles in an iron-based aqueous electrolyte for effective oxygen evolution and mediator reduction reactions under illumination. Several product characterization methods, including an optical oxygen sensor, pressure sensor, gas chromatography, and UV/Vis spectroscopy are used and compared for accurate, high-resolution gas-products and mediator conversion measurements. Advantages of each technique are discussed. A high Faraday efficiency of 97.5±2 % is calculated and the reaction rate limits are investigated.

Raman study of laser-induced heating effects in free-standing silicon nanocrystals.

This paper demonstrates that free-standing silicon nanocrystals (Si NCs) have significantly different thermal conductivity properties compared to Si NCs embedded in a host matrix. The temperatures of Si NCs under laser illumination have been determined by measuring the ratio of the Anti-Stokes to Stokes intensities of the first order Si-Si transverse optical (TO) phonon mode. It is found that large free-standing Si NCs are easily heated up to ∼953 K by the laser light. The laser heating effects are reversible to a large extent, however the nature of the free-standing Si NCs is slightly modified after intensive illumination. The free-standing Si NCs can even be easily melted when exposed to a well-focused laser beam. Under these conditions, the blackbody radiation of the heated Si NCs starts to compete with the detected Raman signals. A simplified model of the heating effects is proposed to study the size dependence of the heated free-standing Si NCs with increasing laser power. It is concluded that the huge red-shift of the Si-Si TO mode observed under intensive laser illumination originates from laser-induced heating effects. In contrast, under similar illumination conditions Si NCs embedded in matrixes are hardly heated due to better thermal conductivity.

Efficient water-splitting device based on a bismuth vanadate photoanode and thin-film silicon solar cells.

A hybrid photovoltaic/photoelectrochemical (PV/PEC) water-splitting device with a benchmark solar-to-hydrogen conversion efficiency of 5.2% under simulated air mass (AM) 1.5 illumination is reported. This cell consists of a gradient-doped tungsten-bismuth vanadate (W:BiVO4 ) photoanode and a thin-film silicon solar cell. The improvement with respect to an earlier cell that also used gradient-doped W:BiVO4 has been achieved by simultaneously introducing a textured substrate to enhance light trapping in the BiVO4 photoanode and further optimization of the W gradient doping profile in the photoanode. Various PV cells have been studied in combination with this BiVO4 photoanode, such as an amorphous silicon (a-Si:H) single junction, an a-Si:H/a-Si:H double junction, and an a-Si:H/nanocrystalline silicon (nc-Si:H) micromorph junction. The highest conversion efficiency, which is also the record efficiency for metal oxide based water-splitting devices, is reached for a tandem system consisting of the optimized W:BiVO4 photoanode and the micromorph (a-Si:H/nc-Si:H) cell. This record efficiency is attributed to the increased performance of the BiVO4 photoanode, which is the limiting factor in this hybrid PEC/PV device, as well as better spectral matching between BiVO4 and the nc-Si:H cell.

Optimization of amorphous silicon double junction solar cells for an efficient photoelectrochemical water splitting device based on a bismuth vanadate photoanode.

A photoelectrochemical water splitting device (PEC-WSD) was designed and fabricated based on cobalt-phosphate-catalysed and tungsten-gradient-doped bismuth vanadate (W:BiVO4) as the photoanode. A simple and cheap hydrogenated amorphous silicon (a-Si:H) double junction solar cell has been used to provide additional bias. The advantage of using thin film silicon (TF-Si) based solar cells is that this photovoltaic (PV) technology meets the crucial requirements for the PV component in PEC-WSDs based on W:BiVO4 photoanodes. TF-Si PV devices are stable in aqueous solutions, are manufactured by simple and cheap fabrication processes and their spectral response, voltage and current density show an excellent match with the photoanode. This paper is mainly focused on the optimization of the TF-Si solar cell with respect to the remaining solar spectrum transmitted through the W:BiVO4 photoanode. The current matching between the top and bottom cells is studied and optimized by varying the thickness of the a-Si:H top cell. We support the experimental optimization of the current balance between the two sub-cells with simulations of the PV devices. In addition, the impact of the light induced degradation of the a-Si:H double junction, the so-called Staebler-Wronski Effect (SWE), on the performance of the PEC-WSD has been studied. The light soaking experiments on the a-Si:H/a-Si:H double junctions over 1000 hours show that the efficiency of a stand-alone a-Si:H/a-Si:H double junction cell is significantly reduced due to the SWE. Nevertheless, the SWE has a significantly smaller effect on the performance of the PEC-WSD.

Efficient solar water splitting by enhanced charge separation in a bismuth vanadate-silicon tandem photoelectrode.

Metal oxides are generally very stable in aqueous solutions and cheap, but their photochemical activity is usually limited by poor charge carrier separation. Here we show that this problem can be solved by introducing a gradient dopant concentration in the metal oxide film, thereby creating a distributed n(+)-n homojunction. This concept is demonstrated with a low-cost, spray-deposited and non-porous tungsten-doped bismuth vanadate photoanode in which carrier-separation efficiencies of up to 80% are achieved. By combining this state-of-the-art photoanode with an earth-abundant cobalt phosphate water-oxidation catalyst and a double- or single-junction amorphous Si solar cell in a tandem configuration, stable short-circuit water-splitting photocurrents of ~4 and 3 mA cm(-2), respectively, are achieved under 1 sun illumination. The 4 mA cm(-2) photocurrent corresponds to a solar-to-hydrogen efficiency of 4.9%, which is the highest efficiency yet reported for a stand-alone water-splitting device based on a metal oxide photoanode.