Zhe Weng

A highly active and stable hydrogen evolution catalyst based on pyrite-structured cobalt phosphosulfide

Rational design and controlled synthesis of hybrid structures comprising multiple components with distinctive functionalities are an intriguing and challenging approach to materials development for important energy applications like electrocatalytic hydrogen production, where there is a great need for cost effective, active and durable catalyst materials to replace the precious platinum. Here we report a structure design and sequential synthesis of a highly active and stable hydrogen evolution electrocatalyst material based on pyrite-structured cobalt phosphosulfide nanoparticles grown on carbon nanotubes. The three synthetic steps in turn render electrical conductivity, catalytic activity and stability to the material. The hybrid material exhibits superior activity for hydrogen evolution, achieving current densities of 10 mA cm−2 and 100 mA cm−2 at overpotentials of 48 mV and 109 mV, respectively. Phosphorus substitution is crucial for the chemical stability and catalytic durability of the material, the molecular origins of which are uncovered by X-ray absorption spectroscopy and computational simulation.

Ternary Hybrid Material for High-Performance Lithium–Sulfur Battery

The rechargeable lithium-sulfur battery is a promising option for energy storage applications because of its low cost and high energy density. The electrochemical performance of the sulfur cathode, however, is substantially compromised because of fast capacity decay caused by polysulfide dissolution/shuttling and low specific capacity caused by the poor electrical conductivities of the active materials. Herein we demonstrate a novel strategy to address these two problems by designing and synthesizing a carbon nanotube (CNT)/NiFe2O4-S ternary hybrid material structure. In this unique material architecture, each component synergistically serves a specific purpose: The porous CNT network provides fast electron conduction paths and structural stability. The NiFe2O4 nanosheets afford strong binding sites for trapping polysulfide intermediates. The fine S nanoparticles well-distributed on the CNT/NiFe2O4 scaffold facilitate fast Li(+) storage and release for energy delivery. The hybrid material exhibits balanced high performance with respect to specific capacity, rate capability, and cycling stability with outstandingly high Coulombic efficiency. Reversible specific capacities of 1350 and 900 mAh g(-1) are achieved at rates of 0.1 and 1 C respectively, together with an unprecedented cycling stability of ∼0.009% capacity decay per cycle over more than 500 cycles.

Electrochemical CO2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution

Exploration of heterogeneous molecular catalysts combining the atomic-level tunability of molecular structures and the practical handling advantages of heterogeneous catalysts represents an attractive approach to developing high-performance catalysts for important and challenging chemical reactions such as electrochemical carbon dioxide reduction which holds the promise for converting emissions back to fuels utilizing renewable energy. Thus, far, efficient and selective electroreduction of CO2 to deeply reduced products such as hydrocarbons remains a big challenge. Here, we report a molecular copper-porphyrin complex (copper(II)-5,10,15,20-tetrakis(2,6-dihydroxyphenyl)porphyrin) that can be used as a heterogeneous electrocatalyst with high activity and selectivity for reducing CO2 to hydrocarbons in aqueous media. At -0.976 V vs the reversible hydrogen electrode, the catalyst is able to drive partial current densities of 13.2 and 8.4 mA cm(-2) for methane and ethylene production from CO2 reduction, corresponding to turnover frequencies of 4.3 and 1.8 molecules·site(-1)·s(-1) for methane and ethylene, respectively. This represents the highest catalytic activity to date for hydrocarbon production over a molecular CO2 reduction electrocatalyst. The unprecedented catalytic performance is attributed to the built-in hydroxyl groups in the porphyrin structure and the reactivity of the copper(I) metal center.

Metal/Oxide Interface Nanostructures Generated by Surface Segregation for Electrocatalysis

Strong metal/oxide interactions have been acknowledged to play prominent roles in chemical catalysis in the gas phase, but remain as an unexplored area in electrocatalysis in the liquid phase. Utilization of metal/oxide interface structures could generate high performance electrocatalysts for clean energy storage and conversion. However, building highly dispersed nanoscale metal/oxide interfaces on conductive scaffolds remains a significant challenge. Here, we report a novel strategy to create metal/oxide interface nanostructures by growing mixed metal oxide nanoparticles on carbon nanotubes (CNTs) and then selectively promoting migration of one of the metal ions to the surface of the oxide nanoparticles and simultaneous reduction to metal. Employing this strategy, we have synthesized Ni/CeO2 nanointerfaces coupled with CNTs. The Ni/CeO2 interface promotes hydrogen evolution catalysis by facilitating water dissociation and modifying the hydrogen binding energy. The Ni/CeO2-CNT hybrid material exhibits superior activity for hydrogen evolution as a result of synergistic effects including strong metal/oxide interactions, inorganic/carbon coupling, and particle size control.

Ultrathin dendrimer–graphene oxide composite film for stable cycling lithium–sulfur batteries

Significance The promise of lithium–sulfur batteries for future electric transportation and stationary energy storage is being limited by their poor cycling stability. Previous approaches to improvement often involve incorporating additional components with significant dead weight or volume in battery structures. We develop an ultrathin functionalized dendrimer–graphene oxide composite film which can be applied to virtually any sulfur cathode to alleviate capacity fading over battery cycling without compromising the energy or power density of the entire battery. The design provides a new strategy for confining lithium polysulfide intermediates and thus stabilizing lithium–sulfur batteries. It also brings a suitable platform for elucidating the underlying materials and surface chemistry. Lithium–sulfur batteries (Li–S batteries) have attracted intense interest because of their high specific capacity and low cost, although they are still hindered by severe capacity loss upon cycling caused by the soluble lithium polysulfide intermediates. Although many structure innovations at the material and device levels have been explored for the ultimate goal of realizing long cycle life of Li–S batteries, it remains a major challenge to achieve stable cycling while avoiding energy and power density compromises caused by the introduction of significant dead weight/volume and increased electrochemical resistance. Here we introduce an ultrathin composite film consisting of naphthalimide-functionalized poly(amidoamine) dendrimers and graphene oxide nanosheets as a cycling stabilizer. Combining the dendrimer structure that can confine polysulfide intermediates chemically and physically together with the graphene oxide that renders the film robust and thin (<1% of the thickness of the active sulfur layer), the composite film is designed to enable stable cycling of sulfur cathodes without compromising the energy and power densities. Our sulfur electrodes coated with the composite film exhibit very good cycling stability, together with high sulfur content, large areal capacity, and improved power rate.

Strong Metal–Phosphide Interactions in Core–Shell Geometry for Enhanced Electrocatalysis

Rational design of multicomponent material structures with strong interfacial interactions enabling enhanced electrocatalysis represents an attractive but underdeveloped paradigm for creating better catalysts for important electrochemical energy conversion reactions. In this work, we report metal-phosphide core-shell nanostructures as a new model electrocatalyst material system where the surface electronic states of the shell phosphide and its interactions with reaction intermediates can be effectively influenced by the core metal to achieve higher catalytic activity. The strategy is demonstrated by the design and synthesis of iron-iron phosphide (Fe@FeP) core-shell nanoparticles on carbon nanotubes (CNTs) where we find that the electronic interactions between the metal and the phosphide components increase the binding strength of hydrogen adatoms toward the optimum. As a consequence, the Fe@FeP/CNT material exhibits exceptional catalytic activity for the hydrogen evolution reaction, only requiring overpotentials of 53-110 mV to reach catalytic current densities of 10-100 mA cm-2.

Electroreduction of CO2 Catalyzed by a Heterogenized Zn–Porphyrin Complex with a Redox-Innocent Metal Center

Transition-metal-based molecular complexes are a class of catalyst materials for electrochemical CO2 reduction to CO that can be rationally designed to deliver high catalytic performance. One common mechanistic feature of these electrocatalysts developed thus far is an electrogenerated reduced metal center associated with catalytic CO2 reduction. Here we report a heterogenized zinc–porphyrin complex (zinc(II) 5,10,15,20-tetramesitylporphyrin) as an electrocatalyst that delivers a turnover frequency as high as 14.4 site–1 s–1 and a Faradaic efficiency as high as 95% for CO2 electroreduction to CO at −1.7 V vs the standard hydrogen electrode in an organic/water mixed electrolyte. While the Zn center is critical to the observed catalysis, in situ and operando X-ray absorption spectroscopic studies reveal that it is redox-innocent throughout the potential range. Cyclic voltammetry indicates that the porphyrin ligand may act as a redox mediator. Chemical reduction of the zinc–porphyrin complex further confirms that the reduction is ligand-based and the reduced species can react with CO2. This represents the first example of a transition-metal complex for CO2 electroreduction catalysis with its metal center being redox-innocent under working conditions.

Ferrocene-Promoted Long-Cycle Lithium–Sulfur Batteries

Confining lithium polysulfide intermediates is one of the most effective ways to alleviate the capacity fade of sulfur-cathode materials in lithium-sulfur (Li-S) batteries. To develop long-cycle Li-S batteries, there is an urgent need for material structures with effective polysulfide binding capability and well-defined surface sites; thereby improving cycling stability and allowing study of molecular-level interactions. This challenge was addressed by introducing an organometallic molecular compound, ferrocene, as a new polysulfide-confining agent. With ferrocene molecules covalently anchored on graphene oxide, sulfur electrode materials with capacity decay as low as 0.014 % per cycle were realized, among the best of cycling stabilities reported to date. With combined spectroscopic studies and theoretical calculations, it was determined that effective polysulfide binding originates from favorable cation-π interactions between Li+ of lithium polysulfides and the negatively charged cyclopentadienyl ligands of ferrocene.

Coupled Metal/Oxide Catalysts with Tunable Product Selectivity for Electrocatalytic CO2 Reduction

One major challenge to the electrochemical conversion of CO2 to useful fuels and chemical products is the lack of efficient catalysts that can selectively direct the reaction to one desirable product and avoid the other possible side products. Making use of strong metal/oxide interactions has recently been demonstrated to be effective in enhancing electrocatalysis in the liquid phase. Here, we report one of the first systematic studies on composition-dependent influences of metal/oxide interactions on electrocatalytic CO2 reduction, utilizing Cu/SnOx heterostructured nanoparticles supported on carbon nanotubes (CNTs) as a model catalyst system. By adjusting the Cu/Sn ratio in the catalyst material structure, we can tune the products of the CO2 electrocatalytic reduction reaction from hydrocarbon-favorable to CO-selective to formic acid-dominant. In the Cu-rich regime, SnOx dramatically alters the catalytic behavior of Cu. The Cu/SnOx-CNT catalyst containing 6.2% of SnOx converts CO2 to CO with a high faradaic efficiency (FE) of 89% and a jCO of 11.3 mA·cm-2 at -0.99 V versus reversible hydrogen electrode, in stark contrast to the Cu-CNT catalyst on which ethylene and methane are the main products for CO2 reduction. In the Sn-rich regime, Cu modifies the catalytic properties of SnOx. The Cu/SnOx-CNT catalyst containing 30.2% of SnOx reduces CO2 to formic acid with an FE of 77% and a jHCOOH of 4.0 mA·cm-2 at -0.99 V, outperforming the SnOx-CNT catalyst which only converts CO2 to formic acid in an FE of 48%.