Hydrogen from wet air and sunlight in a tandem photoelectrochemical cell

A solid-state photoelectrochemical (SSPEC) cell is an attractive approach for solar water splitting, especially when it comes to monolithic device design. In a SSPEC cell the electrodes distance is minimized, while the use of polymer-based membranes alleviates the need for liquid electrolytes, and at the same time they can separate the anode from the cathode. In this work, we have made and tested, firstly, a SSPEC cell with a Pt/C electrocatalyst as the cathode electrode, under purely gaseous conditions. The anode was supplied with air of 80% relative humidity (RH) and the cathode with argon. Secondly, we replaced the Pt/C cathode with a photocathode consisting of 2D photocatalytic g-C₃N₄, which was placed in tandem with the photoanode (tandem-SSPEC). The tandem configuration showed a three-fold enhancement in the obtained photovoltage and a steady-state photocurrent density. The mechanism of operation is discussed in view of recent advances in surface proton conduction in absorbed water layers. The presented SSPEC cell is based on earth-abundant materials and provides a way towards systems of artificial photosynthesis, especially for areas where water sources are scarce and electrical grid infrastructure is limited or nonexistent. The only requirements to make hydrogen are humidity and sunlight.     

共价有机框架材料及其在关键核素分离中的应用进展

共价有机框架材料（COFs）是一类由共价键连接的多孔晶态材料。因具有单体链接方式灵活、结构可调、活性位点丰富、比表面积大、理化性质相对稳定等特点，它们在气体储存与分离、能量储存、催化和光电学领域受到了广泛的关注。本文主要从结构设计、合成方法及功能化、材料的分析表征和晶形控制等方面概括地介绍了COFs材料。在此基础上，综述了COFs材料在关键核素分离方面的研究进展，并展望了其在核素分离领域的应用前景和今后的研究方向。     

B Cells with a Senescent-Associated Secretory Phenotype Accumulate in the Adipose Tissue of Individuals with Obesity

Senescent cells accumulate in the adipose tissue (AT) of individuals with obesity and secrete multiple factors that constitute the senescence-associated secretory phenotype (SASP). This paper aimed at the identification of B cells with a SASP phenotype in the AT, as compared to the peripheral blood, of individuals with obesity. Our results show increased expression of SASP markers in AT versus blood B cells, a phenotype associated with a hyper-metabolic profile necessary to support the increased immune activation of AT-derived B cells as compared to blood-derived B cells. This hyper-metabolic profile is needed for the secretion of the pro-inflammatory mediators (cytokines, chemokines, micro-RNAs) that fuel local and systemic inflammation.     

高碘酸盐的活化及降解水体有机污染物研究进展

根据高碘酸盐活化方式、活化机理和相关自由基种类等方面,叙述了国内外高碘酸盐高级氧化体系降解水体有机污染物方面的工作。基于氧化剂为高碘酸盐的高级氧化技术氧化能力强,能在较宽的pH范围内高效降解包括抗氧化能力极强的全氟辛酸(PFOA)在内的多种有机污染物,在水处理领域具有较好的应用潜力。依据目前的研究现状,结合实际需求,认为进行废水处理的小试或者中试、优化活化理论研究,以及明确各活性物质对有机物选择性降解的机理,是将来需要关注的问题以及研究方向。     

Recent Development of Photothermal Agents (PTAs) Based on Small Organic Molecular Dyes

Photothermal therapy (PTT) has attracted great attention due to its noninvasive and effective use against cancer. Various photothermal agents (PTAs) including organic and inorganic PTAs have been developed in the last decades. Organic PTAs based on small-molecule dyes exhibit great potential for future clinical applications considering their good biocompatibility and easy chemical modification or functionalization. In this review, we discuss the recent progress of organic PTAs based on small-molecule dyes for enhanced PTT. We summarize the strategies to improve the light penetration of PTAs, methods to enhance their photothermal conversion efficiency, how to optimize PTAs’ delivery into deep tumors, and how to resist photobleaching under repeated laser irradiation. We hope that this review can rouse the interest of researchers in the field of PTAs based on small-molecule dyes and help them to fabricate next-generation PTAs for noninvasive cancer therapy.     

Efficient dye-sensitized solar cells based on CNTs and Zr-doped TiO2 nanoparticles

The light scattering, harvesting and adsorption effects in dye-sensitized solar cells (DSSCs) are studied by preparation of coated carbon nanotubes (CNTs) with TiO₂ and Zr-doped TiO₂ nanoparticles in the forms of mono- and double-layer cells. X-ray diffraction (XRD) analysis reveals that the phase composition of Zr-doped TiO₂ electrode is a mixture of anatase and rutile phases with major rutile content, whereas it is the same mixture with major anatase content for coated CNTs with TiO₂. Furthermore, the average crystallite size of Zr-doped TiO₂ electrode is slightly decreased with Zr introduction. Field emission scanning electron microscope (FE-SEM) images show that the porosity of Zr-doped TiO₂ electrodes is higher than that of undoped electrode, enhancing dye adsorption. UV–visible spectroscopy analysis reveals that the absorption onset of Zr-doped TiO₂ electrodes is slightly shifted to longer wavelength (the red-shift) in comparison with that of undoped TiO₂ electrode. Moreover, the band gap energy of TiO₂ nanoparticles is decreased by Zr introduction, enhancing light absorption. It is found that electron injection of monolayer TiO₂ electrode is improved by introduction of 0.025 mol% Zr, resulted in enhancement of its power conversion efficiency (PCE) up to 6.81% compared with 6.17% for pure TiO₂ electrode. Moreover, electron transport and light scattering are enhanced by incorporation of 0.025 wt% coated CNTs with TiO₂ in the over-layer of double layer electrode. Therefore, double layer solar cell composed of 0.025 mol% Zr-doped TiO₂ nanoparticles as the under-layer and mixtures of these nanoparticles and 0.025 wt% coated CNTs with TiO₂ as the over-layer shows the highest PCE of 8.19%.     

Performance improvement of conventional and inverted polymer solar cells with hydrophobic fluoropolymer as nonvolatile processing additive

The morphology of the photoactive layer critically affects the performance of the bulk heterojunction polymer solar cells (PSCs). To control the morphology, we introduced a hydrophobic fluoropolymer polyvinylidene fluoride (PVDF) as nonvolatile additive into the P3HT:PCBM active layer. The effect of PVDF on the surface and the bulk morphology were investigated by atomic force microscope and transmission electron microscopy, respectively. Through the repulsive interactions between the hydrophilic PCBM and the hydrophobic PVDF, much more uniform phase separation with good P3HT crystallinity is formed within the active layer, resulting enhanced light harvesting and improved photovoltaic performance in conventional devices. The PCE of the conventional device can improve from 2.40% to 3.07% with PVDF additive. The PVDF distribution within the active layer was investigated by secondary ion mass spectroscopy, confirming a bottom distribution of PVDF. Therefore, inverted device structure was designed, and the PCE can improve from 2.81% to 3.45% with PVDF additive. Our findings suggest that PVDF is a promising nonvolatile processing additive for high performance polymer solar cells.     

Dihydrotanshinone,a Natural Diterpenoid,Preserves Blood-Retinal Barrier Integrity via P2X7 Receptor

Activation of P2X7 signaling, due to high glucose levels, leads to blood retinal barrier (BRB) breakdown, which is a hallmark of diabetic retinopathy (DR). Furthermore, several studies report that high glucose (HG) conditions and the related activation of the P2X7 receptor (P2X7R) lead to the over-expression of pro-inflammatory markers. In order to identify novel P2X7R antagonists, we carried out virtual screening on a focused compound dataset, including indole derivatives and natural compounds such as caffeic acid phenethyl ester derivatives, flavonoids, and diterpenoids. Molecular Mechanics/Generalized Born Surface Area (MM/GBSA) rescoring and structural fingerprint clustering of docking poses from virtual screening highlighted that the diterpenoid dihydrotanshinone (DHTS) clustered with the well-known P2X7R antagonist JNJ47965567. A human-based in vitro BRB model made of retinal pericytes, astrocytes, and endothelial cells was used to assess the potential protective effect of DHTS against HG and 2′(3′)-O-(4-Benzoylbenzoyl)adenosine-5′-triphosphate (BzATP), a P2X7R agonist, insult. We found that HG/BzATP exposure generated BRB breakdown by enhancing barrier permeability (trans-endothelial electrical resistance (TEER)) and reducing the levels of ZO-1 and VE-cadherin junction proteins as well as of the Cx-43 mRNA expression levels. Furthermore, HG levels and P2X7R agonist treatment led to increased expression of pro-inflammatory mediators (TLR-4, IL-1β, IL-6, TNF-α, and IL-8) and other molecular markers (P2X7R, VEGF-A, and ICAM-1), along with enhanced production of reactive oxygen species. Treatment with DHTS preserved the BRB integrity from HG/BzATP damage. The protective effects of DHTS were also compared to the validated P2X7R antagonist, JNJ47965567. In conclusion, we provided new findings pointing out the therapeutic potential of DHTS, which is an inhibitor of P2X7R, in terms of preventing and/or counteracting the BRB dysfunctions elicited by HG conditions.     

Investigation of LSM-8YSZ cathode within an all ceramic SOFC. Part I: Chemical interactions

This work focuses on a novel, co-sintered, all-ceramic solid oxide fuel cell (SOFC) concept. The objective is the understanding of interaction and degradation mechanisms of the cathode and current collector layers within the design during co-sintering. Half cells consisting of silicate mechanical support, lanthanum strontium manganite (LSM) current collector, LSM mixed with 8 mol% yttria-stabilized zirconia (8YSZ) composite cathode and 8YSZ electrolyte were co-sintered at 1150 °C < T < 1250 °C. Crystallographically stable LSM compositions within the design were identified. However, the cathode and silicate/electrolyte interacted by interdiffusion of Zn (gas diffusion) and Mn (solid diffusion), and by the formation of several reaction phases (between silicate and cathode only). Introducing silicate poisoning decreased the electrochemical performance of the cell by around 40%. This is likely due to the formation of the Zn- and Mn-rich phase in the cathode, but may also be caused by a higher ohmic resistance of the current collector.     

Carbon supported bimetallic Ru‐Co catalysts for H2 production through NaBH4 and NH3BH3 hydrolysis

This work investigates the effect of the addition of small amounts of Ru (0.5‐1 wt%) to carbon supported Co (10 wt%) catalysts towards both NaBH₄ and NH₃BH₃ hydrolysis for H₂ production. In the sodium borohydride hydrolysis, the activity of Ru‐Co/carbon catalysts was sensibly higher than the sum of the activities of corresponding monometallic samples, whereas for the ammonia borane hydrolysis, the positive effect of Ru‐Co systems with regard to catalytic activity was less evident. The performances of Ru‐Co bimetallic catalysts correlated with the occurrence of an interaction between Ru and Co species resulting in the formation of smaller ruthenium and cobalt oxide particles with a more homogeneous dispersion on the carbon support. It was proposed that Ru^°, formed during the reduction step of the Ru‐Co catalysts, favors the H₂ activation, thus enhancing the reduction degree of the cobalt precursor and the number of Co nucleation centers. A subsequent reduction of cobalt and ruthenium species also occurs in the hydride reaction medium, and therefore the state of the catalyst before the catalytic experiment determines the state of the active phase formed in situ. The different relative reactivity of the Ru and Co active species towards the two investigated reactions accounted for the different behavior towards NaBH₄ and NH₃BH₃ hydrolysis.