Latest ArticlesCO oxidation at ceria surfaces has been studied for decades, and many efforts have been devoted to understanding the effect of surface reduction on the catalytic activity. In this work, we theoretically studied the CO oxidation on the clean and reduced CeO2(111) surfaces using different surface cells to determine the relationships between the reduction degrees and calculated reaction energetics. It is found that the calculated barrier for the direct reaction between CO and surface lattice O drastically decreases with the increase of surface reduction degree. From electronic analysis, we found that the surface reduction can lead to the occurrence of localized electrons at the surface Ce, which affects the charge distribution at surface O. As the result, the surface O becomes more negatively charged and therefore more active in reacting with CO. This work then suggests that the localized 4f electron reservoir of Ce can act as the "pseudo-anion" at reduced CeO2 surfaces to activate surface lattice O for catalytic oxidative reactions.
Here, the selective adsorption behaviors of guest molecule COR in two hexamer host grids were investigated by means of scanning tunnelling microscope (STM). The assembled structures of small functional organic molecules TTBTA and TATBA were thermodynamically stable. Interestingly, the introduction of the guest molecule COR destroyed the original hexamer structure of TTBTA and combined with it to form a new triangular host-guest system. Different from TTBTA, the introduction of the guest molecule COR did not affect the six-membered ring structure of TATBA. Furthermore, the co-assembly structure of TTBTA/TATBA/COR was established and the guest molecule COR showed preferential adsorption to the TATBA host grid. Density functional theory (DFT) calculations had been performed to disclose the mechanism of the involved assemblies.
Stable solid electrolyte interphase (SEI) has been well established to be critical for the reversible operation of Li (ion) batteries, yet our understanding of its mechanical properties currently remains incomplete. Here, we used an electrochemical quartz crystal microbalance combined with dissipation monitoring (EQCM-D) to investigate SEI formation. By quantitatively estimating in-situ, the change in mass, shear modulus, and viscosity of the SEI, we show that the SEI formation in propylene carbonate (PC)- and ethylene carbonate/diethyl carbonate (EC/DEC)-based electrolytes involves the growth of a rigid layer followed by a viscoelastic layer, whereas a distinct "one-layer" rigid model is applicable to the SEI formulated in tetraethylene glycol dimethyl ether (TEGDME)-based electrolyte. With the continuous formation of the SEI, its shear modulus decreases accompanied by an increase in viscosity. In TEGDME, the lightest/thinnest SEI (mass lower than in PC by a factor of nine) yet having the greatest stiffness (more than five times that in PC) is obtained. We attribute this behavior to differences in the chemical composition of the SEIs, which have been revealed by tracking the mass-change-per-mole-of-electron-transferred using EQCM-D and further confirmed by X-ray photoelectron spectroscopy.
The potassium-ion batteries (PIBs) have become the promising energy storage devices due to their relatively moderate cost and plenteous potassium resources. Whereas, the main drawback of PIBs is unsatisfactory electrochemical performance induced by the larger ionic radius of potassium ion. Herein, we report a well-designed, uniform-dispersed, and morphology-controllable zinc sulfide (ZnS) quantum dots loading on graphene as an anode in the PIBs. The directed uniform dispersion of the in-situ growing ZnS quantum dots (~2.8 nm in size) on graphene can mitigate the volume effect during the insertion-extraction process and shorten the migration path of potassium ions. As a result, the battery exhibits superior cycling stability (350.4 mAh/g over 200 cycles at 0.1 A/g) and rate performance (98.8 mAh/g at 2.0 A/g). We believe the design of active material with quantum dot-minimized size provides a novel route into PIBs and contributes to eliminating the major electrode failure issues of the system.
Photoelectrochemical (PEC) water splitting is a promising approach for renewable hydrogen production. However, the practical PEC solar-to-fuel conversion efficiency is still low owing to poor light absorption and rapid recombination of charge carriers in photoelectrode. In this work, we report a ternary photoanode with simultaneously enhancement of light absorption and water oxidation efficiency by introducing copper phthalocyanine (CuPc) and nickel iron-layered double hydroxide (NiFe-LDH) on TiO2 (denoted as TiO2/CuPc/NiFe-LDH). An experimental study reveals that CuPc loading on TiO2 bring strong visible light absorption; NiFe-LDH as an oxygen evolution reaction catalyst efficiently accelerates the surface water oxidation reaction. This synergistic effect of CuPc and NiFe-LDH gives enhanced photocurrent density (2.10 mA/cm2 at 0.6 V vs. SCE) and excellent stability in the ternary TiO2/CuPc/NiFeLDH photoanode.
By pairing two fluorophores according to their optical properties such as absorption spectral overlap and absorptivity, fluorescent quantum yield and emission spectral separation, a bifunctional fluorescent probe, TQBF-NBD, was rationally designed and synthesized to discriminatively sense Hcy/Cys and GSH with good selectivity and sensitivity. It is noted that this probe could work under a single-wavelength excitation and displayed a mega-large Stokes shift. TQBF-NBD reacted with Hcy/Cys to give a mixed green-red fluorescence and displayed a red fluorescence upon the treatment with GSH. Distinguishable imaging of intracellular Hcy/Cys from GSH with the help of TQBF-NBD was realized in living cells and zebrafish.
Herein, copper ion doped calcium alginate (Cu2+/CaAlg) composite hydrogel filtration membranes were prepared by using natural polymer sodium alginate (NaAlg) as raw material. The thermal stability and structure of the composite membranes were characterized by thermogravimetric analysis and infrared spectroscopy. The mechanical strength, anti-fouling performance, hydrophilicity and filtration performance of the membrane were studied. The results show that Cu2+/CaAlg hydrogel membrane has excellent mechanical properties and thermal stability. The anti-swelling ability of the membrane was greatly enhanced by doping Cu2+. After three alternate filtration cycles, the flux recovery rate of Cu2+/CaAlg hydrogel membrane can still reach 85%, indicating that the membrane has good anti-pollution performance. When the operation pressure was 0.1 MPa, the rejection of coomassie brilliant blue G250 reached 99.8% with a flux of 46.3 L m-2 h-1, while the Na2SO4 rejectionwas less than 10.0%. The Cu2+/CaAlg membrane was recycled after 24 h in the filtration process, and its flux and rejection rate did not decrease significantly, indicating that the hydrogel membrane has long-term application potential. The Cu2+/CaAlg membrane has a wide range of applications prospect in dye desalination, fine separation and biopharmaceutical technology fields.
Developing highly efficient nickel or iron based hydroxide electrocatalysts is primary essential but challenging for oxygen evolution reaction (OER) at ultra-high current densities. Herein, we developed a facile method to prepare nitrogen and iron doped nickel(Ⅱ) hydroxide nanosheets on self-supported conductive nickel foam (denoted as Fe, N-Ni(OH)2/NF) through ammonia hydrothermal and impregnation methods. Owing to the optimization of the electronic structure by nitrogen doping and the strong synergistic effect between Fe and Ni(OH)2, the three-dimensional (3D) Fe, N-Ni(OH)2/NF nanosheets delivered superior electrocatalytic OER performances in basic solution with low potentials of 1.57V and 1.59V under 500mA/cm2 and 1000mA/cm2 respectively and robust operation for 10 h with ignored activity decay, comparing well with the potentials of previously reported NiFe based electrocatalysts as well as the benchmark commercial Ir/C/NF. In-situ Raman spectroscopy revealed that the main active species were NiOOH during the OER process. The present results are expected to provide new insights into the study of OER process towards ultra-high current densities.
Constructing 3D multifunctional conductive framework as stable sulfur cathode contributes to develop advanced lithium-sulfur (Li-S) batteries. Herein, a freestanding electrode with nickel foam framework and nitrogen doped porous carbon (PC) network is presented to encapsulate active sulfur for Li-S batteries. In such a mutually embedded architecture with high stability, the interconnected carbon network and nickel foam matrix can expedite ionic/electronic transport and sustain volume variations of sulfur. Furthermore, rationally designed porous structures provide sufficient internal space and large surface area for high active sulfur loading and polar polysulfides anchoring. Benefiting from the synergistic superiority, the Ni/PC-S cathode exhibits a high initial capacity of around 1200 mAh/g at 0.2 C, excellent rate performance, and high cycling stability with a low decay rate of 0.059% per cycle after 500 cycles. This work provides a useful strategy to exploit freestanding porous framework for diverse applications.
Radiotherapy is commonly used to treat advanced pancreatic cancers and can improve survival by 2 months in combination with gemcitabine. However, prognosis and survival improvement remain unsatisfactory, and effective therapies are urgently needed. Piperlongumine has been demonstrated to have therapeutic potentials against various cancers. In this study, we synthesized a series of piperlongumine derivatives and provided evidence that piperlongumine derivatives could be used as effective radiosensitizers in pancreatic cancer. Two compounds enhanced the radiosensitivity of Panc-1 and SW1990 cells. In a pancreatic bi-flank xenograft tumor model, they significantly inhibited tumor growth. Piperlongumine derivatives could induce reactive oxygen species (ROS) expression and regulate the Keap1-Nrf2 protective pathway with enhancement of radiation-induced DNA damage, G2/M-phase cell cycle arrest, and apoptosis. Collectively, our data offer a proof of concept for the use of piperlongumine derivatives as a novel class of radiosensitizers for the treatment of pancreatic cancer.