Rational Design of CoOOH/α-Fe2O3/SnO2 for Boosted Photoelectrochemical Water Oxidation: The Roles of Underneath SnO2 and Surface CoOOH.

Hematite (α-Fe2O3) photoanode is a promising candidate for efficient PEC solar energy conversion. However, the serious charge recombination together with the sluggish water oxidation kinetics of α-Fe2O3 still restricts its practical application in renewable energy systems. In this work, a CoOOH/α-Fe2O3/SnO2 photoanode was fabricated, in which the ultrathin SnO2 underlayer is deposited on the fluorine-doped tin oxide (FTO) substrate, α-Fe2O3 nanorod array is the absorber layer, and CoOOH nanosheet is the surface modifier, respectively. The resulting CoOOH/α-Fe2O3/SnO2 exhibited excellent PEC water splitting with a high photocurrent density of 2.05 mA cm-2 at 1.23 V vs RHE in the alkaline electrolyte, which is ca. 3.25 times that of bare α-Fe2O3. PEC characterizations demonstrated that SnO2 not only could block hole transport from α-Fe2O3 to FTO substrate but also could efficiently enhance the light-harvesting property and reduce the surface states by controlling the growth process of α-Fe2O3, while the CoOOH overlayer as cocatalysts could rapidly extract the photogenerated holes and provide catalytic active sites for water oxidation. Benefiting from the synergistic effects of SnO2 and CoOOH, the efficiency of the charge recombination and the overpotential for water oxidation of α-Fe2O3 are obviously decreased, resulting in the boosted PEC efficiency for water oxidation. The rational design and simple fabrication strategy display great potentials to be used for other PEC systems with excellent efficiency.

CdS/ZnS Heterostructured Porous Composite with Enhanced Visible Light Photocatalysis.

Fabrication of semiconductor composites consisting of multicomponent or multiphase heterojunctions is a very effective strategy to design highly active photocatalyst systems. Here we present a facile design to fabricate novel CdS/ZnS heterostructured porous sheet-like nanocomposite based on a cation-exchanged hydrothermal procedure. Micro-structural analyses reveal that the product is a kind of heterostructured composite with porous structure and high crystallinity. The composite nanosheets exhibited enhanced visible-light photoactivity compared with pure ZnS or CdS. Among them, sample of Cd0.45Zn0.55S gave the highest degradation rate of about 99% under visible-light irradiation within 60 min when 10 mg of the sample was added into 50 mL of methyl orange in aqueous solution (10 mg/L). The enhanced photocatalytic activity was presumed to result from the direct photoinduced interfacial charge transfer (IFCT) from the valence band (VB) of ZnS to CdS.

Synergetic effect of dual cocatalysts in photocatalytic H2 production on Pd-IrOx/TiO2: a new insight into dual cocatalyst location.

Introducing appropriate dual cocatalysts is one of the most efficient strategies to improve the photocatalytic activity. Herein, we investigated the promotion effect of dual cocatalysts on TiO2 for hydrogen production. Compared with the Pd/TiO2 and Ir/TiO2 with the individual cocatalyst, TiO2 coloaded with Pd and Ir species exhibited an obviously enhanced H2 production activity and reduced CO/H2 ratio. XPS and IR spectra of CO adsorption analysis indicated that the dual cocatalysts on TiO2 were actually composed of Pd(0) and partially oxidized IrOx, which acted as the reduction and oxidation cocatalysts, respectively. Interestingly, EDX elemental mappings of Pd and Ir indicated that the two elements on TiO2 were inclined to depositing together. The synergetic effect of reduction and oxidation cocatalysts with their intimate contact is proposed to contribute to the high H2 production activity, which is different from the common view that the reduction and oxidation sites should be spatially separated to avoid the charge recombination.

Surface coordination induced a quasi p-n junction for efficient visible light driven degradation of tetracycline over hydroxyapatite.

The removal of antibiotics from aquatic solutions remains a global environmental challenge. In this work, the photocatalytic removal of a typical antibiotic-tetracycline (TC) using hydroxyapatite (HAp) as a catalyst was investigated. It was impressive that TC could be efficiently degraded by HAp under visible light irradiation, even though both HAp and TC exhibited poor harvesting in visible light region. The experimental and theoretical explorations were undertaken to thoroughly investigate the underlying mechanism of visible light degradation of TC over HAp. The results indicated that the formed TC-HAp complexes via surface coordination played an important role as photosensitizers for the visible light response. Together with the formation of a quasi p-n junction via band alignment, the photogenerated electrons in the highest unoccupied molecular orbital (HOMO) of TC-HAp were excited to the lowest unoccupied molecular orbital (LUMO) and subsequently migrated to the conduction band of HAp to achieve the efficient charge separation. Superoxide radicals and holes were found to be the major active species for TC degradation. The toxicity evaluation showed that TC could be transferred to the lower toxic intermediates, and deep oxidation with prolonged reaction time was necessary to eliminate the toxicity of TC. This work demonstrates the surface coordination with subsequent quasi p-n junction mechanism of TC degradation over HAp under visible light, which will stimulate us to explore new efficient photocatalytic systems for the degradation of various contaminants.

Hematite decorated with nanodot-like cobalt (oxy)hydroxides for boosted photoelectrochemical water oxidation.

Photoelectrochemical (PEC) water splitting has been considered as an alternative process to produce green hydrogen. However, the energy conversion efficiency of PEC systems was still limited by the inefficient photoanode. Cocatalysts decoration is regarded as an efficient strategy for improving PEC performance of photoanode. In this work, nanodot-like cobalt (oxy)hydroxides was rationally decorated on hematite to fabricate CoOOH/Fe2O3 photoanode. The resulted CoOOH/Fe2O3 exhibits a high photocurrent density of 1.92 mA cm-2 at 1.23 V vs. RHE, which is 2.6 times than that of bare Fe2O3. In addition, the onset potential displays a cathodic shift of ca. 110 mV, indicating that CoOOH can efficiently accelerate water oxidation kinetics over Fe2O3. The comprehensive PEC and electrochemical characterizations reveal that CoOOH could not only provide abundant accessible Co active sites for water oxidation, but also could passivate the surface states of Fe2O3, thus increase the carrier density and decrease the interfacial resistance. As a result, the PEC water oxidation performance over Fe2O3 was significantly boosted. This work supports that the roles of CoOOH cocatalyst is generic and such CoOOH could be used for other semiconductor-based photoanodes for outstanding PEC water splitting performance.

Characteristic of molecular subtype based on lysosome-associated genes reveals clinical prognosis and immune infiltration of gastric cancer.

Background: Lysosome are involved in nutrient sensing, cell signaling, cell death, immune responses and cell metabolism, which play an important role in the initiation and development of multiple tumors. However, the biological function of lysosome in gastric cancer (GC) has not been revealed. Here, we aim to screen lysosome-associated genes and established a corresponding prognostic risk signature for GC, then explore the role and underlying mechanisms. Methods: The lysosome-associated genes (LYAGs) were obtained from MSigDB database. Differentially expressed lysosome-associated genes (DE-LYAGs) of GC were acquired based on the TCGA database and GEO database. According to expression profiles of DE-LYAGs, we divided the GC patients into different subgroups and then explored tumor microenvironment (TME) landscape and immunotherapy response in LYAG subtypes using GSVA, ESTIMATE and ssGSEA algorithms. Univariate Cox regression analysis, LASSO algorithm and multivariate Cox regression analysis were adopted to identify the prognostic LYAGs and then establish a risk model for patients with GC. The Kaplan-Meier analysis, Cox regression analysis and ROC analysis were utilized to evaluate the performance of the prognostic risk model. Clinical GC specimens were also used to verify the bioinformatics results by qRT-PCR assay. Results: Thirteen DE-LYAGs were obtained and utilized to distinguish three subtypes in GC samples. Expression profiles of the 13 DE-LYAGs predicted prognosis, tumor-related immunological abnormalities and pathway dysregulation in these three subtypes. Furthermore, we constructed a prognostic risk model for GC based on DEG in the three subtypes. The Kaplan-Meier analysis suggested that higher risk score related to short OS rate. The Cox regression analysis and ROC analysis indicated that risk model had independent and excellent ability in predicting prognosis of GC patients. Mechanistically, a remarkable difference was observed in immune cell infiltration, immunotherapy response, somatic mutation landscape and drug sensitivity. qRT-PCR results showed that compared with corresponding adjacent normal tissues, most screened genes showed significant abnormal expressions and the expression change trends were consistent with the bioinformatics results. Conclusions: We established a novel signature based on LYAGs which could be served as a prognostic biomarker for GC. Our study might provide new insights into individualized prognostication and precision treatment for GC.

Sensitive photoelectrochemical sensing of glucose using hematite decorated with NiAl-layered double hydroxides.

Hematite (α-Fe2O3) is a promising photoelectrode material for photoelectrochemical (PEC) sensors. However, it still suffers from serious surface charge recombination and slow interfacial charge transfer kinetics. In this work, NiAl-layered double hydroxides decorated on α-Fe2O3 (NiAl-LDH/α-Fe2O3) was successfully fabricated via a facile hydrothermal method. The NiAl-LDH/α-Fe2O3 exhibits excellent PEC response toward glucose, with a good linear range from 0.01 to 2 mM, a high sensitivity of 274.7 µA·mM-1·cm-2 and a low detection limit of 0.005 mM. NiAl-LDH/α-Fe2O3 PEC sensor could be used for glucose determination in various food samples, such as bread, toast and glucose oral solution, which achieved comparable results with that of HPLC. PEC and electrochemical characterizations indicate NiAl-LDH could act as and/or provide active sites for glucose detection, enlarge the band bending and decrease the charge transfer resistance, thus significantly improve the PEC response of α-Fe2O3 toward glucose.

Insights into the multirole CoAl layered double hydroxide on boosting photoelectrochemical activity of hematite: Application to hydrogen peroxide sensing.

As an important compound in many industrial and biological processes, hydrogen peroxide (H2O2) would cause harmfulness to human health at high concentration level. It thus is urgent to develop highly sensitive and selective sensors for practical H2O2 detection in the fields of water monitoring, food quality control, and so on. In this work, CoAl layered double hydroxide ultrathin nanosheets decorated hematite (CoAl-LDH/α-Fe2O3) photoelectrode was successfully fabricated by a facile hydrothermal process. CoAl-LDH/α-Fe2O3 displays the relatively wide linear range from 1 to 2000 µM with a high sensitivity of 132.0 µA mM-1 cm-2 and a low detection limit of 0.04 µM (S/N ≥ 3) for PEC detection of H2O2, which is superior to other similar α-Fe2O3-based sensors in literatures. The (photo)electrochemical characterizations, such as electrochemical impedance spectroscopy, Mott-Schottky plot, cyclic voltammetry, open circuit potential and intensity modulated photocurrent spectroscopy, were used to investigate the roles of CoAl-LDH on the improved PEC response of α-Fe2O3 toward H2O2. It revealed that, CoAl-LDH could not only passivate the surface states and enlarge the band bending of α-Fe2O3, but also could act as trapping centers for holes and followed by as active sites for H2O2 oxidation, thus facilitated the charge separation and transfer. The strategy for boosting PEC response would be help for the further development of semiconductor-based PEC sensors.

Feasibility of using ammonium iron (II) sulphate to passivate hexavalent chromium in polluted soil.

ABSTRACTThe use of ammonium iron (II) sulphate ((NH4)2Fe(SO4)2) to remediate soil contaminated with Cr (VI) was assessed. (NH4)2Fe(SO4)2 effectively remediated soil contaminated with Cr (VI) and, acted as a fertilizer by supplying nitrogen because it contains ammonium. The effects of the (NH4)2Fe(SO4)2 dose, water content, pH of the soil and the contact time were investigated. The amount of Cr (VI) leached from the most-polluted soil, determined using a leaching toxicity procedure using optimized conditions, was 347.64 mg kg-1 when the soil was untreated and 6.74 mg kg-1 when the soil was treated with (NH4)2Fe(SO4)2. Bio-utilizable Cr contributed 59.44% and 0.16% of the total Cr contents of the untreated and treated soil, respectively. The relatively stable Cr species contributed 24.92% and 98.38% of the total Cr contents of the untreated and treated soil, respectively. The results indicated that adding (NH4)2Fe(SO4)2 markedly decreased the risk of Cr being released from heavily contaminated soil by decreasing the availability of Cr in the soil. Overall, the results indicated that adding (NH4)2Fe(SO4)2 causes some Cr (VI) in contaminated soil to be reduced to Cr (III), and to form a precipitate, which decreases the risk of Cr being released. (NH4)2Fe(SO4)2 can be applied to soil contaminated with Cr (VI) on a large scale because it is cheap and simple to achieve.

Photoelectrochemical sensing and mechanism investigation of hydrogen peroxide using a pristine hematite nanoarrays.

In this paper, a facile hydrothermal combined with subsequent two-step post-calcination method was used to fabricate hematite (α-Fe2O3) nanoarrays on fluorine-doped SnO2 glass (FTO). The morphology, crystalline phase, optical property and surface chemical states of the fabricated α-Fe2O3 photoelectrode were characterized by scanning electron microscopy, X-ray diffraction, ultraviolet visible spectroscopy and X-ray photoelectron spectroscopy correspondingly. The α-Fe2O3 photoelectrode exhibits excellent photoelectrochemical (PEC) response toward hydrogen peroxide (H2O2) in aqueous solutions, with a low detection limit of 20 µM (S/N = 3) and wide linear range (0.01-0.09, 0.3-4, and 6-16 mM). Additionally, the α-Fe2O3 photoelectrode shows satisfying reproducibility, stability, selectivity and good feasibility for real samples. Mechanism analysis indicates, comparing with H2O, H2O2 possesses much more fast reaction kinetics over α-Fe2O3 surface, thus the recombination of photogenerated charges are reduced, followed by much more photogenerated electrons are migrated to the counter electrode via external circuit. The insight on the enhanced photocurrent, which is corelative to the concentration of H2O2 in aqueous solution, will stimulate us to further optimize the surface structure of α-Fe2O3 to gain highly efficient α-Fe2O3 based sensors.

Surface defect-engineered silver silicate/ceria p-n heterojunctions with a flower-like structure for boosting visible light photocatalysis with mechanistic insight.

Charge carrier separation of photocatalysts can be accelerated by p-n heterojunctions and surface defect engineering. Here, novel silver silicate/ceria p-n heterojunction photocatalysts with a hierarchical flower-like structure were successfully synthesized through an in situ deposition-precipitation method in which p-type silver silicate (Ag6Si2O7) nanoparticles were evenly decorated on the sheets of n-type ceria (CeO2) nanoflowers prepared via an ice-bath coprecipitation process. Mott-Schottky plots and morphological studies indicated that p-n heterojunctions were constructed between Ag6Si2O7 and CeO2. This led to the generation of abundant surface defects (Ce3+ ions or oxygen vacancies) in the heterojunctions as confirmed by XPS and Raman. The photocatalytic properties are markedly improved under visible light irradiation and can be regulated by the Ag6Si2O7 content in the composites. The sample with 40 wt% Ag6Si2O7 loading had optimal photocatalytic elimination efficiency for the colorless contaminant tetracycline, the cationic dye rhodamine B, and the anionic dye methyl orange. As evidenced by various characterization techniques, the decoration of Ag6Si2O7 nanoparticles can promote the formation of a surface defect structure, increase visible light harvesting, and improve the separation of charge carriers driven by the internal electric field established between two semiconductors, thus leading to a remarkably enhanced photocatalytic activity. This work offers a reliable strategy for designing efficient p-n heterojunctions for photocatalytic applications in energy and the environment.

Plasmon-mediated nonradiative energy transfer from a conjugated polymer to a plane of graphene-nanodot-supported silver nanoparticles: an insight into characteristic distance.

Hybrid nanostructures comprising conjugated polymers (CPs) and plasmonic metals show excellent performance in light harvesting. However, the energy transfer mechanism of the CP film to nearby metal nanoparticles, especially knowledge of the characteristic distance, is still unclear. Here, quenching of the emission of a CP film in proximity to a monolayer of graphene-nanodot-supported silver nanoparticles (GND-Ag NPs) is investigated. Uniform Ag NPs with D = 3.2 nm were grown on GNDs in situ under mild light irradiation, and a series of bilayer structures of GND-Ag NPs/CPs were constructed by spin-coating blue, green and red light-emitting poly(9,9-dioctylfluorene) (PFO), poly(9,9-dioctylfluorene-alt-benzothiadiazole) (F8BT) and poly[2-methoxy-5-(2'-ethylhexyloxy)-p-phenylene vinylene] (MEH-PPV),respectively, on top of the GND-Ag NP plane. The spacer distance was controlled by the layers of assembled polyelectrolytes. Both steady and transient photoluminescence (PL) spectra showed emission quenching of the bilayer structures, providing the maximum efficiency of 99% for the F8BT films. The surface density of GND-Ag NPs and the spacer distance-dependent PL quenching data were analyzed within the plasmonic resonant energy transfer model, and the extracted characteristic distances are 6 nm, 3 nm and 10 nm for the PFO, F8BT and MEH-PPV systems, respectively. Current-sensing atomic force microscopy shows that the GND-Ag NPs/F8BT film exhibits enhanced electrical conductivity. These results are believed to be important for the development of plasmonic enhanced polymer photovoltaics and photocatalysis.

Conversion of Biomass Derivatives to Electricity in Photo Fuel Cells using Undoped and Tungsten-doped Bismuth Vanadate Photoanodes.

The photo fuel cell (PFC) is a promising technology for simultaneously converting solar energy and bioenergy into electricity. Here, we present a miniature air-breathing PFC that uses either BiVO4 or W-doped BiVO4 as the photoanode and a Pt/C catalyst as the air-breathing cathode. The PFC exhibited excellent performance under solar illumination and when fed with several types of biomaterial. We found the PFC performance could be significantly enhanced using W-doping into the BiVO4 photoanode. With glucose as the fuel and simulated sunlight (AM 1.5 G) as the light source, the open-circuit voltage increased from 0.74 to 0.92 V, the short-circuit current density rose from 0.46 to 1.62 mA cm(-2) , and the maximum power density was boosted from 0.05 to 0.38 mW cm(-2) , compared to a PFC using undoped BiVO4 as the anode.

Photocatalytic aerobic oxidation of amines to imines on BiVO4 under visible light irradiation.

BiVO4 was found to be an efficient photocatalyst under visible light irradiation for selective oxidation of amines to imines with high activity (99% conversion) and selectivity (up to 99%) using oxygen as an oxidant.

Selective photocatalytic conversion of glycerol to hydroxyacetaldehyde in aqueous solution on facet tuned TiO2-based catalysts.

Glycerol is selectively converted to hydroxyacetaldehyde (HAA) and H2 in aqueous solution on TiO2-based photocatalysts. The product selectivity was verified to be strongly dependent on the facets of TiO2. Rutile with high percentage of {110} facets results in over 90% superior selectivity of HAA, while anatase with {001} or {101} facets gives only 16% and 49% selectivity for HAA, respectively.

The role of glutathione on shape control and photoelectrical property of cadmium sulfide nanorod arrays.

Well-aligned CdS nanorod arrays (CdS NRs) with ~100 nm in diameter and ~700 nm in length were fabricated on FTO (fluorine-doped tin oxide) substrate by using glutathione as capping agents. The growth of CdS NRs was studied in details by exploring the roles of each active binding group in glutathione. The thiol group in glutathione plays an important role in forming a compact CdS nanocrystal film, upon which the nanorods grow subsequently via the synergetic effect of thiol and dicarboxyl groups in glutathione. The influence of surface passivation with glutathione on the photoelectrical property of CdS NRs was also tested. The results revealed that glutathione ligands encapsulated in the surfaces of CdS NRs act as insulating barriers between CdS NRs and solution, hindering charge transport. Hybrid photovoltaic cells of FTO/CdS NRs/P3HT (poly(3-hexylthiophene))/Au were then assembled. The performance of the photovoltaic devices was increased with increasing the length of the as-prepared CdS nanorods and further enhanced to the highest efficiency of 0.373% after the thermal sulfuration treatment.