A High Efficiency Aluminum-Ion Battery Using an AlCl3-Urea Ionic Liquid Analogue Electrolyte

In recent years, impressive advances in harvesting renewable energy have led to pressing demand for the complimentary energy storage technology. Here, a high coulombic efficiency (~ 99.7%) Al battery is developed using earth-abundant aluminum as the anode, graphite as the cathode, and a cheap ionic liquid analogue electrolyte made from a mixture of AlCl3 and urea in 1.3 : 1 molar ratio. The battery displays discharge voltage plateaus around 1.9 V and 1.5 V (average discharge = 1.73 V) and yielded a specific cathode capacity of ~73 mAh g-1 at a current density of 100 mA g-1 (~ 1.4 C). High coulombic efficiency over a range of charge-discharge rates and stability over ~150-200 cycles was easily demonstrated. In-situ Raman spectroscopy clearly showed chloroaluminate anion intercalation/deintercalation of graphite in the cathode side during charge/discharge and suggested the formation of a stage 2 graphite intercalation compound when fully charged. Raman spectroscopy and nuclear magnetic resonance suggested the existence of AlCl4-, Al2Cl7- anions, and [AlCl2. (urea)n]+ cations in the urea/AlCl3 electrolyte when an excess of AlCl3 was present. Aluminum deposition therefore proceeded through two pathways, one involving Al2Cl7- anions and the other involving [AlCl2.(urea)n]+ cations. This battery is a promising prospect for a future high performance, low cost energy storage device

Improving the Photocurrent in Quantum-Dot-Sensitized Solar Cells by Employing Alloy PbxCd1−xS Quantum Dots as Photosensitizers

Ternary alloy PbxCd1−xS quantum dots (QDs) were explored as photosensitizers for quantum-dot-sensitized solar cells (QDSCs). Alloy PbxCd1−xS QDs (Pb0.54Cd0.46S, Pb0.31Cd0.69S, and Pb0.24Cd0.76S) were found to substantially improve the photocurrent of the solar cells compared to the single CdS or PbS QDs. Moreover, it was found that the photocurrent increases and the photovoltage decreases when the ratio of Pb in PbxCd1−xS is increased. Without surface protecting layer deposition, the highest short-circuit current density reaches 20 mA/cm2 under simulated AM 1.5 illumination (100 mW/cm2). After an additional CdS coating layer was deposited onto the PbxCd1−xS electrode, the photovoltaic performance further improved, with a photocurrent of 22.6 mA/cm2 and an efficiency of 3.2%

Development of Nanoparticle Sensitized Solar Cells

In this thesis, I have been working with the development of nanoparticle sensitized solar cells. In the subarea of quantum dot sensitized solar cells (QDSCs), I have investigated type-II quantum dots (QDs), quantum rods (QRs) and alloy QDs, and developed novel redox couples as electrolytes. I have also proposed upconversion nanoparticles as energy relay materials for dye-sensitized solar cells (DSCs). Colloidal ZnSe/CdS type-II QDs were applied for QDSCs for the first time. The interesting features of those refer to that their photoelectrons and photoholes are located on the different parts of the dot, namely in the CdS shell and in the ZnSe core, respectively. That spatial separation between photoelectrons and photoholes can so effectively enhance the charge extraction efficiency, thus facilitating the electron injection, and also effectively expand the absorption spectrum. All these characteristics contribute to a high photon to current conversion efficiency. Furthermore, a comparison between the photovoltaic performance of ZnSe/CdS and CdS/ZnSe QDSCs shows that the electron distribution is important for the electron injection of the QDs. Colloidal CdS/CdSe QRs were applied to quantum rod-sensitized solar cells (QRSCs). They showed a higher electron injection efficiency than the analogous QDSCs. It is concluded that reduction of the carrier confinement dimensions of the nanoparticles can improve the electron injection efficiency of the nanoparticle sensitized solar cells. Two types of organic electrolytes based on the redox couples of McMT-/BMT (OS1) and TMTU/TMTU-TFO (OS2) were used for the QDSCs. By reducing the charge recombination between the electrolyte and the counter electrode, the fill factor and the photovoltage of these QDSCs were significantly improved, resulting in a higher efficiency for the studied solar cells than that with a commonly used inorganic electrolyte. Ternary-alloy PbxCd1-xS QDs used as photosensitizers for QDSCs were found to improve the photocurrent compared to the corresponding CdS and PbS QDs. By considering the effect of different ratios of Pb to Cd in thePbxCd1-xS QDs on the photovoltaic performance it was discovered that the photocurrent increases and the photovoltage decreases with the increase of the ratio in a certain range. Upconversion (UC) nanoparticles provide a strategy to develop panchromatic solar cells. Three types of UC nanoparticles employed by DSCs were confirmed to work as energy relay materials for effectively extending the light-harvesting spectrum to the near-infrared (NIR) region. They were also found to play a role as scattering centers to enhance the photovoltaic performance of the solar cells.QC 20131002</p

The Study of II-VI Semiconductor Nanocrystals Sensitized Solar Cells

Semiconductor nanocrystals, also referred to as quantum dots (QDs), have been the focus of great scientific and technological efforts in solar cells, as a result of their advantages of low-cost, photostability, high molar extinction coefficients and size-dependent optical properties. Due to the multi-electron generation effect, the theoretically maximum efficiency of quantum dots-sensitized solar cells (QDSCs) is as high as 44%, which is much higher than that of dye-sensitized solar cells (DSCs). Thus QDSCs have a clear potential to overtake the efficiency of all other kinds of solar cells. In recent years, the efficiency of QDSCs has been improved very quickly to around 5%. It is however still much lower than that of DSCs. The low efficiency is mostly caused by the high electron loss between electrolyte and electrodes and the lack of an efficient electrolyte. In this thesis, we have been working to enhance the performance of QDSCs with II-VI group nanocrystals by increasing the electron injection efficiency from QDs to TiO2 and developing new redox couples in electrolyte. To increase the electron injection, firstly, colloidal ZnSe/CdS type-II QDs were synthesized and applied for QDSCs for the first time, whose photoelectron and photohole are located on CdS shell and ZnSe core, respectively. The spatial separation between photoelectron and photohole can effectively enhance the charge extraction efficiency, facilitating electron injection, and also effectively expand the absorption spectrum. All these characteristics contribute to the high photon to current conversion efficiency. Furthermore, a comparison between the performances of ZnSe/CdS and CdS/ZnSe QDs shows that the electron distribution is important for the electron injection of the QDs in QDSCs. Secondly, colloidal CdS/CdSe quantum rods (QRs) were applied to a quantum rod-sensitized solar cell (QRSCs) that showed a higher electron injection efficiency than analogous QDSCs. It is concluded that reducing the carrier confinement dimensions of nanocrystals can improve electron injection efficiency of nanocrystal sensitized solar cells. In this thesis, two types of organic electrolytes based McMT-/BMT and TMTU/TMTU-TFO were used for QDSCs. By reducing the charge recombination between the electrolyte and counter electrode, fill factor (FF) of these QDSCs was significantly improved. At the same time, the photovoltages of the QDSCs were remarkably increased. As a result, the overall conversion efficiency of QDSCs based on the new electrolytes was much higher than that with a commonly used inorganic electrolyte. In addition, CdS QDSCs on NiO photoelectrode were studied which shows a n-type photovoltaic performance. This performance is attributed to the formation of a thin Cd metal film before CdS QDs formation on NiO. Since the CB edge of CdS sits between the Fermi level and the CB edge of Cd metal, a much strong electron transfer between Cd and CdS QD is obtained, resulting in the observed n-type photovoltaic performance of these CdS/NiO QDSCs.QC 2012042

Boosting the Electrocatalytic Activity of Nickel-Iron Layered Double Hydroxide for the Oxygen Evolution Reaction byTerephthalic Acid

The development of a new type of oxygen evolution reaction (OER) catalyst to reduce the energy loss in the process of water electrolysis is of great significance to the realization of the industrialization of hydrogen energy storage. Herein, we report the catalysts of NiFe double-layer hydroxide (NiFe-LDH) mixed with different equivalent terephthalic acid (TPA), synthesized by the hydrothermal method. The catalyst synthesized with the use of the precursor solution containing one equivalent of TPA shows the best performance with the current density of 2 mA cm−2 at an overpotential of 270 mV, the Tafel slope of 40 mV dec−1, and excellent stable electrocatalytic performance for OER. These catalysts were characterized in a variety of methods. X-ray diffraction (XRD), Fourier Transform Infrared Spectrometer (FTIR), and Raman spectrum proved the presence of TPA in the catalysts. The lamellar structure and the uniform distribution of Ni and Fe in the catalysts were observed by a scanning electron microscope (SEM) and a transmission electron microscope (TEM). In X-ray photoelectron spectroscopy (XPS) of NiFe-LDH with and without TPA, the changes in the peak positions of Ni and Fe spectra indicate strong electronic interactions between TPA and Ni and Fe atoms. These results suggest that a certain amount of TPA can boost catalytic activity

Klebsiella pneumoniae Induces Inflammatory Bowel Disease Through Caspase-11–Mediated IL18 in the Gut Epithelial CellsSummary

Background &amp; Aims: Klebsiella pneumoniae (KLP), a Gram-negative bacterium belonging to the family of Enterobacteriaceae, is a common cause of antimicrobial-resistant opportunistic infections in hospitalized patients. KLP can colonize in the human gastrointestinal tract, especially in patients with inflammatory bowel diseases. However, effects of KLP on the onset and development of inflammatory bowel disease remain unclear. Methods: We analyzed the relationship between Mayo indexes of ulcerative colitis and KLP using quantitative reverse-transcription polymerase chain reaction and endoscopy. Using caspase-1/11-/-, NLRP3-/-, NLRC4-/-, interleukin (IL)18-/-, and IL22-/- mice, we showed that KLP could induce colitis through caspase-11–mediated release of mature IL18. Through in vitro gut organoid culture, we determined the mechanism for KLP to induce colitis. Results: We first found that there was a positive relationship between the Mayo indexes of ulcerative colitis and KLP. Then, we isolated a strain of KLP, named Klebsiella pneumoniae J (KLPJ), from the colon tissues of patients with colitis. This strain of bacteria could induce the production of mature IL18 in colon epithelial cells and gut organoids, and also induce colitis and promote dextran sodium sulfate–mediated colitis. Using caspase-1/11-/-, NLRP3-/-, NLRC4-/-, IL18-/-, and IL22-/- mice, we showed that KLPJ-mediated colitis occurred through activation of caspase-11, and was dependent on IL18 and partly on IL22. Our data also showed that lipopolysaccharide from KLPJ could bind with caspase-11 to induce mature IL18 in mouse and human colon organoids. Conclusions: KLPJ from the colon tissues of patients with ulcerative colitis can colonize the colon, activate caspase-11 inflammasomes, and contribute to intestinal inflammation

Improved Performance of Colloidal CdSe Quantum Dot-Sensitized Solar Cells by Hybrid Passivation

A hybrid passivation strategy is employed to modify the surface of colloidal CdSe quantum dots (QDs) for quantum dot-sensitized solar cells (QDSCs), by using mercaptopropionic acid (MPA) and iodide anions through a ligand exchange reaction in solution. This is found to be an effective way to improve the performance of QDSCs based on colloidal QDs. The results show that MPA can increase the coverage of the QDs on TiO₂ electrodes and facilitate the hole extraction from the photoxidized QDs, and simultaneously, that the iodide anions can remedy the surface defects of the CdSe QDs and thus reduce the recombination loss in the device. This hybrid passivation treatment leads to a significant enhancement of the power conversion efficiency of the QDSCs by 41%. Furthermore, an optimal ratio of iodide ions to MPA was determined for favorable hybrid passivation; results show that excessive iodine anions are detrimental to the loading of the QDs. This study demonstrates that the improvement in QDSC performance can be realized by using a combination of different functional ligands to passivate the QDs, and that ligand exchange in solution can be an effective approach to introduce different ligands

A ruthenium-based catalyst on carbon electrodes for electrochemical water splitting

Electrochemical water splitting constitutes one of the most promising strategies for converting water into hydrogen-based fuels, and this technology is predicted to play a key role in our transition towards a carbon-neutral energy economy. To enable the design of cost-effective electrolysis cells based on this technology, new and more efficient anodes with augmented water splitting activity and stability will be required. Herein, we report an active molecular Ru-based catalyst for electrochemically-driven water oxidation and two simple methods for preparing anodes by attaching this catalyst onto multi-walled carbon nanotubes. The anodes modified with the molecular catalyst were characterized by a broad toolbox of microscopy and spectroscope techniques, and interestingly no RuO2 formation was detected during electrocatalysis over 4 h. These results demonstrate that the herein presented strategy can be used to prepare anodes that rival the performance of state-of-the-art metal oxide anodes

Survival outcomes in locally advanced dMMR rectal cancer: surgery plus adjunctive treatment vs. surgery alone

Abstract Background Recent studies have shown that deficient mismatch repair (dMMR) rectal cancer may be related to treatment resistance, resulting in a worse prognosis than proficient MMR (pMMR) rectal cancer. The purpose of this study was to explore whether surgery plus other treatments (radiotherapy and chemotherapy) can bring more benefits to these patients than surgery alone. Methods A retrospective study of 168 patients with rectal adenocarcinoma who underwent total mesorectal excision was conducted using immunohistochemical methods to determine MMR status and a propensity score matching model to minimize potential confounding factors between subgroups of patients with different treatment regimens. Kaplan–Meier analysis, log-rank tests, and Cox regression models were used to assess overall survival (OS) and disease-free survival (DFS) in patient subgroups. Results Only 6.9% (n = 168) of patients in the total cohort had dMMR rectal adenocarcinoma, and the most common cause of dMMR was a PMS2 deletion (103, 61.3%). The median DFS of the surgery alone group was 45.7 months (IQR, 40.9 to 77.8), and the median DFS of the surgery plus other treatment group was 43.9 months (IQR, 14.2 to 80.1). The surgery alone group was superior to the surgery plus other treatment group (HR, 0.16; 95% CI, 0.07 to 0.38; p = 0.005). There was no significant difference in OS (45.8 (IQR, 41.0 to 79.8) vs. 45.9 (IQR, 38.5 to 80.3)) between the two groups (HR, 0.57; 95% CI, 0.23 to 1.40; p = 0.263). Conclusions For patients with locally advanced dMMR rectal adenocarcinoma, compared with surgery alone, surgery plus other treatment options (radiotherapy and chemotherapy) do not grant long-term survival benefits but rather shorten DFS

Simultaneous Multiple Wavelength Upconversion in a Core–Shell Nanoparticle for Enhanced Near Infrared Light Harvesting in a Dye-Sensitized Solar Cell

The efficiency of most photovoltaic devices is severely limited by near-infrared (NIR) transmission losses. To alleviate this limitation, a new type of colloidal upconversion nanoparticles (UCNPs), hexagonal core–shell-structured β-NaYbF₄:Er³⁺(2%)/NaYF₄:Nd³⁺(30%), is developed and explored in this work as an NIR energy relay material for dye-sensitized solar cells (DSSCs). These UCNPs are able to harvest light energy in multiple NIR regions, and subsequently convert the absorbed energy into visible light where the DSSCs strongly absorb. The NIR-insensitive DSSCs show compelling photocurrent increases through binary upconversion under NIR light illumination either at 785 or 980 nm, substantiating efficient energy relay by these UCNPs. The overall conversion efficiency of the DSSCs was improved with the introduction of UCNPs under simulated AM 1.5 solar irradiation