A room temperature rechargeable Li2O-based lithium-air battery enabled by a solid electrolyte.

A lithium-air battery based on lithium oxide (Li2O) formation can theoretically deliver an energy density that is comparable to that of gasoline. Lithium oxide formation involves a four-electron reaction that is more difficult to achieve than the one- and two-electron reaction processes that result in lithium superoxide (LiO2) and lithium peroxide (Li2O2), respectively. By using a composite polymer electrolyte based on Li10GeP2S12 nanoparticles embedded in a modified polyethylene oxide polymer matrix, we found that Li2O is the main product in a room temperature solid-state lithium-air battery. The battery is rechargeable for 1000 cycles with a low polarization gap and can operate at high rates. The four-electron reaction is enabled by a mixed ion-electron-conducting discharge product and its interface with air.

Gold-like activity copper-like selectivity of heteroatomic transition metal carbides for electrocatalytic carbon dioxide reduction reaction.

An overarching challenge of the electrochemical carbon dioxide reduction reaction (eCO2RR) is finding an earth-abundant, highly active catalyst that selectively produces hydrocarbons at relatively low overpotentials. Here, we report the eCO2RR performance of two-dimensional transition metal carbide class of materials. Our results indicate a maximum methane (CH4) current density of -421.63 mA/cm2 and a CH4 faradic efficiency of 82.7% ± 2% for di-tungsten carbide (W2C) nanoflakes in a hybrid electrolyte of 3 M potassium hydroxide and 2 M choline-chloride. Powered by a triple junction photovoltaic cell, we demonstrate a flow electrolyzer that uses humidified CO2 to produce CH4 in a 700-h process under one sun illumination with a CO2RR energy efficiency of about 62.3% and a solar-to-fuel efficiency of 20.7%. Density functional theory calculations reveal that dissociation of water, chemisorption of CO2 and cleavage of the C-O bond-the most energy consuming elementary steps in other catalysts such as copper-become nearly spontaneous at the W2C surface. This results in instantaneous formation of adsorbed CO-an important reaction intermediate-and an unlimited source of protons near the tungsten surface sites that are the main reasons for the observed superior activity, selectivity, and small potential.

Kinetically Stable Oxide Overlayers on Mo3 P Nanoparticles Enabling Lithium-Air Batteries with Low Overpotentials and Long Cycle Life.

The main drawbacks of today's state-of-the-art lithium-air (Li-air) batteries are their low energy efficiency and limited cycle life due to the lack of earth-abundant cathode catalysts that can drive both oxygen reduction and evolution reactions (ORR and OER) at high rates at thermodynamic potentials. Here, inexpensive trimolybdenum phosphide (Mo3 P) nanoparticles with an exceptional activity-ORR and OER current densities of 7.21 and 6.85 mA cm-2 at 2.0 and 4.2 V versus Li/Li+ , respectively-in an oxygen-saturated non-aqueous electrolyte are reported. The Tafel plots indicate remarkably low charge transfer resistance-Tafel slopes of 35 and 38 mV dec-1 for ORR and OER, respectively-resulting in the lowest ORR overpotential of 4.0 mV and OER overpotential of 5.1 mV reported to date. Using this catalyst, a Li-air battery cell with low discharge and charge overpotentials of 80 and 270 mV, respectively, and high energy efficiency of 90.2% in the first cycle is demonstrated. A long cycle life of 1200 is also achieved for this cell. Density functional theory calculations of ORR and OER on Mo3 P (110) reveal that an oxide overlayer formed on the surface gives rise to the observed high ORR and OER electrocatalytic activity and small discharge/charge overpotentials.

Oxygen Functionalized Copper Nanoparticles for Solar-Driven Conversion of Carbon Dioxide to Methane.

Solar conversion of carbon dioxide (CO2) into hydrocarbon fuels offers a promising approach to fulfill the world's ever-increasing energy demands in a sustainable way. However, a highly active catalyst that can also tune the selectivity toward desired products must be developed for an effective process. Here, we present oxygen functionalized copper (OFn-Cu) nanoparticles as a highly active and methane (CH4) selective catalyst for the electrocatalytic CO2 reduction reaction. Our electrochemical results indicate that OFn-Cu (5 nm) nanoparticles with an oxidized layer at the surface reach a maximum CH4 formation current density and turnover frequency of 36.24 mA/cm2 and of 0.17 s-1 at the potential of -1.05 V vs RHE, respectively, exceeding the performance of existing Cu and Cu-based catalysts. Characterization results indicate that the surface of the OFn-Cu nanoparticles consists of an oxygen functionalized layer in the form of Cu2+ (CuO) separated from the underneath elemental Cu by a Cu+ (Cu2O) sublayer. Density functional theory calculations also confirm that presence of the O site at the CuO (101) surface is the main reason for the enhanced activity and selectivity. Using this catalyst, we have demonstrated a flow cell with an active area of 25 cm2 that utilizes solar energy to produce 7.24 L of CH4 after 10 h of continuous process at a cell power density of 30 mW/cm2.

Oxidation of toluene in humid air by metal oxides supported on γ-alumina.

Monometallic and bimetallic supported metal oxides catalysts on γ-alumina were prepared by heterogeneous deposition-precipitation. The γ-alumina used as a support was synthesized by the sol-gel and the co-precipitation methods. Supports and catalysts were characterized by Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), field-emission scanning electron microscopy (FESEM), transmission electron microscopy (TEM), and X-ray photoelectron spectroscopy (XPS). The performance of the prepared catalysts was studied for total oxidation of toluene in air at different relative humidity and oxidation temperatures. Efficiency of bimetallic catalysts for deep oxidation of toluene was higher than copper oxide supported on γ-alumina. Although increasing the lanthanum, cobalt, and nickel loading on the support led to a modified catalyst surface and morphology, the catalytic activity of bimetallic catalysts decreased with increasing lanthanum, cobalt, and nickel content due to the reduced amount of copper oxide which has a higher activity for oxidation of volatile organic compounds. The γ-alumina prepared by the sol-gel method using ethanol as a solvent (AlSE) was the best support and La-Cu/AlSE had the best performance (toluene removal efficiency >90%). In addition, the presence of water vapor in the feed had a negative effect on toluene conversion.