Construction of Ultrafine PtIr Clusters Supported on Co3O4 Nanoflowers for Enhanced Overall Water Splitting.

Green hydrogen production through electrochemical overall water splitting has suffered from sluggish oxygen evolution reaction (OER) kinetics, inferior conversion efficiency, and high cost. Herein, ultrafine PtIr clusters are synthesized via an electrodeposition method and decorated on the Co3O4 nanoflowers assembled by nanowires (PtIr-Co3O4). The encouraging performances in electrochemical OER and hydrogen evolution reaction (HER) are achieved over the PtIr-Co3O4 catalyst, with the overpotentials as low as 410 and 237 mV at 100 mA cm-2, respectively, outperforming the commercial IrO2 and Pt/C catalysts. Due to the ultralow loading of PtIr clusters, the PtIr-Co3O4 catalyst exhibits 1270 A gIr -1 for OER at the overpotential of 400 mV. Our detailed analyses also show that the strong interactions between the ultrafine PtIr clusters and the Co3O4 nanoflowers enable the PtIr-Co3O4 catalyst to afford 10 mA cm-2 for the overall water splitting at the potential of 1.57 V, accompanied by high durability for 100 h.

Generalized Rapid Synthesis of Supported Nanocluster Catalyst for Mild Hydrogenation of Phenol toward KA Oil.

Homogeneous and nanometric metal clusters with unique electronic structures are promising for catalysis, however, common synthesis techniques for metal clusters suffer from large size and even metal nanocrystals attributing to their high surface energy and unsaturated configurations. Herein, a generalized rapid annealing strategy for synthesizing a series of supported metal clusters as superior catalysts is developed. Remarkably, TiO2 supported platinum nanoclusters (Pt NC/TiO2 ) exhibits the excellent catalytic activity to realize phenol hydrogenation under mild conditions. The complete phenol conversion rate and 100% selectivity toward KA oil are achieved in aqueous solution at room temperature and normal pressure. Semi-continuous scale up production of KA oil is successfully performed under mild conditions. Such excellent performance mainly originates from the partial reconstruction of Pt NC/TiO2 in aqueous phenol solution. Considering that the phenol can be produced from lignin, this study underpins a facile, sustainable, and economical route to synthesize nylon from biomass.

Ice as Solid Electrolyte To Conduct Various Kinds of Ions.

Water, considered as a universal solvent to dissolve salts, has been extensively studied as liquid electrolyte in electrochemical devices. The water/ice phase transition at around 0 °C presents a common phenomenon in nature, however, the chemical and electrochemical behaviors of ice have rarely been studied. Herein, we discovered that the ice phase provides efficient ionic transport channels and therefore can be applied as generalized solid-state ionic conductor. Solid state ionic conducting ices (ICIs) of Li+ , Na+ , Mg2+ , Al3+ , K+ , Mn2+ , Fe2+ , Co2+ , Ni2+ , Cu2+ , and Zn2+ , frozen from corresponding sulphate solutions, exhibit ionic conductivities ranging from ≈10-7  S cm-1 (Zn2+ ) to ≈10-3  S cm-1 (Li+ ) at temperatures spanning from -20 °C to -5 °C. The discovery of ICIs opens new insight to design and fabrication of solid-state electrolytes that are simple, inexpensive, and versatile.

Direct Blow-Spinning of Nanofibers on a Window Screen for Highly Efficient PM2.5 Removal.

Particulate matter (PM) pollution has caused many serious public health issues. Whereas indoor air protection usually relies on expensive and energy-consuming filtering devices, direct PM filtration by window screens has attracted increasing attention. Recently, electrospun polymer nanofiber networks have been developed as transparent filters for highly efficient PM2.5 removal; however, it remains challenging to uniformly coat the nanofibers on window screens on a large scale and with low cost. Here, we report a blow-spinning technique that is fast, efficient, and free of high voltages for the large-scale direct coating of nanofibers onto window screens for indoor PM pollution protection. We have achieved a transparent air filter of 80% optical transparency with >99% standard removal efficiency level for PM2.5. A test on a real window (1 m × 2 m) in Beijing has proven that the nanofiber transparent air filter acquires excellent PM2.5 removal efficiency of 90.6% over 12 h under extremely hazy air conditions (PM2.5 mass concentration > 708 µg/m3). Moreover, we show that the nanofibers can be readily coated on the window screen for pollution protection and can be easily removed by wiping the screen after hazardous days.

Ice Melting to Release Reactants in Solution Syntheses.

Aqueous solution syntheses are mostly based on mixing two solutions with different reactants. It is shown that freezing one solution and melting it in another solution provides a new interesting strategy to mix chemicals and to significantly change the reaction kinetics and thermodynamics. For example, a precursor solution containing a certain concentration of AgNO3 was frozen and dropped into a reductive NaBH4 solution at about 0 °C. The ultra-slow release of reactants was successfully achieved. An ice-melting process can be used to synthesize atomically dispersed metals, including cobalt, nickel, copper, rhodium, ruthenium, palladium, silver, osmium, iridium, platinum, and gold, which can be easily extended to other solution syntheses (such as precipitation, hydrolysis, and displacement reactions) and provide a generalized method to redesign the interphase reaction kinetics and ion diffusion in wet chemistry.

Strategies to Improve the Oxygen Reduction Reaction Activity on Pt-Bi Bimetallic Catalysts: A Density Functional Theory Study.

Decreasing the level of use of Pt in proton exchange membrane fuel cells is of great research interest both academically and industrially. In this work, we systematically studied the oxygen reduction reaction (ORR) following the four-electron association mechanism at various Pt-Bi surfaces with density functional theory calculations. The results showed that the introduction of Bi changes the potential-determining step of ORR. Moreover, the hydroxy adsorption free energy (GOH*) can be used as a descriptor of ORR activity, and 0.74 eV is the ideal GOH* for it to reach its maximum. Notably, we also found that the tensile strain introduced by Bi and electron transfer between Pt and Bi synergize to modulate the d-band of Pt to contract, shift downward, and break the 5d96s1 valence electron configuration of Pt, and accordingly, PtBi(100), with the lowest d-band center, gives the best ORR activity, which is even slightly higher than that of Pt(111).

An amorphous ultrathin iridium/carbon catalyst realizing efficient electrochemical hydrogen evolution.

An amorphous 1.1 nm Ir/C catalyst exhibits ultralow overpotentials of 10 and 64 mV for the hydrogen evolution reaction at current densities of 10 and 100 mA cm-2, together with 117 A mg-1 mass activity and outstanding long-term durability, superior to those of the commercial Pt/C catalyst.

Hierarchical Ni-Mo-P nanoarrays toward efficient urea oxidation reaction.

The urea oxidation reaction (UOR), which possesses a low theoretical potential and superior kinetics, is an attractive substitute for the anodic oxygen evolution reaction (OER) in overall water splitting; however, the implementation of hydrogen production in overall urea splitting is impeded by the deficiency of highly efficient, durable and cost-effective catalysts. Herein, we fabricated an Ni2P-MoP2 heterostructure with a hierarchical structure grown on carbon paper (Ni-Mo-P/CP), which exhibited robust activity and outstanding durability for the electrocatalytic oxidation of urea. The Ni-Mo-P/CP catalyst possessed an ultralow potential of 1.39 V to obtain the current density of 100 mA cm-2, small Tafel slope (27 mV dec-1) and long-term durability with almost no decay within 15 h. The experimental characterization revealed that the optimized electronic structure and the synergistic effect of abundant exposed active sites in the Ni-Mo-P/CP catalyst contribute to the efficient UOR catalytic activity. This work enriches the candidate catalysts for the UOR and promotes the industrial development of hydrogen production.

Large Piezoelectric Strain in Sub-10 Nanometer Two-Dimensional Polyvinylidene Fluoride Nanoflakes.

Functional polymers such as polyvinylidene fluoride (PVDF) and its copolymers, which exhibit room-temperature piezoelectricity and ferroelectricity in two-dimensional (2D) limit, are promising candidates to substitute hazardous lead-based piezoceramics for flexible nanoelectronic and electromechanical energy-harvesting applications. However, realization of many polymers including PVDF in ultrathin 2D nanostructures with desired crystal phases and tunable properties remains challenging due to ineffective conventional synthesis methods. Consequently, it has remained elusive to obtain optimized piezoelectric performance of PVDF particularly in sub-10 nm regimes. Taking advantage of its high flexibility and easy processing, we fabricate ultrathin PVDF nanoflakes with thicknesses down to 7 nm by using a hot-pressing method. This thermo-mechanical strategy simultaneously induces robust thermodynamic α to electroactive ß-phase transformation, with ß fraction as high as 92.8% in sub-10 nm flakes. Subsequently, piezoelectric studies performed by using piezoresponse force microscopy reveal an excellent piezoelectric strain of 0.7% in 7 nm film and the highest piezoelectric coefficient ( d33) achieved is -68 pm/V for 50 nm-thick nanoflakes, which is 13% higher than the piezoresponse from 50 nm-thick PZT nanofilms. Our results further suggest thickness modulation as an effective strategy to tune the piezoelectric performance of PVDF and affirm its supremacy over conventional piezoceramics especially at nanoscale. This work aims not only to help understand fundamental piezoelectricity of pure PVDF in sub-10 nm regimes but also provides an opportunity to realize other polymer-based 2D nanocrystals.

-60 °C solution synthesis of atomically dispersed cobalt electrocatalyst with superior performance.

Temperature can govern morphologies, structures and properties of products from synthesis in solution. A reaction in solution at low temperature may result in different materials than at higher temperature due to thermodynamics and kinetics of nuclei formation. Here, we report a low-temperature solution synthesis of atomically dispersed cobalt in a catalyst with superior performance. By using a water/alcohol mixed solvent with low freezing point, liquid-phase reduction of a cobalt precursor with hydrazine hydrate is realized at -60 °C. A higher energy barrier and a sluggish nucleation rate are achieved to suppress nuclei formation; thus atomically dispersed cobalt is successfully obtained in a catalyst for oxygen reduction with electrochemical performance superior to that of a Pt/C catalyst. Furthermore, the atomically dispersed cobalt catalyst is applied in a microbial fuel cell to obtain a high maximum power density (2550 ± 60 mW m-2) and no current drop upon operation for 820 h.

Boosting the Electrocatalytic Water Oxidation Performance of CoFe2O4 Nanoparticles by Surface Defect Engineering.

Spinel oxides have attracted widespread interest for electrocatalytic applications owing to their unique crystal structure and properties. The surface structure of spinel oxides significantly influences the electrocatalytic performance of spinel oxides. Herein, we report a Li reduction strategy that can quickly tune the surface structure of CoFe2O4 (CFO) nanoparticles and optimize its electrocatalytic oxygen evolution reaction (OER) performance. Results show that a large number of defective domains have been successfully introduced at the surface of CFO nanopowders after Li reduction treatment. The defective CFO nanoparticles demonstrate significantly improved electrocatalytic OER activity. The OER potential observed a negative shift from 1.605 to 1.513 V at 10 mA cm-2, whereas the Tafel slope is greatly decreased to 42.1 mV dec-1 after 4 wt % Li reduction treatment. This efficient Li reduction strategy can also be applied to engineer the surface defect structure of other material systems and broaden their applications.

Ultralow-temperature photochemical synthesis of atomically dispersed Pt catalysts for the hydrogen evolution reaction.

Efficient control of nucleation is a prerequisite for the solution-phase synthesis of nanocrystals. Although the thermodynamics and kinetics of the formation of metal nanoparticles have been largely investigated, fully suppressing the nucleation in solution synthesis remains a major challenge due to the high surface free energy of isolated atoms. In this article, we largely decreased the reaction temperature for ultraviolet (UV) photochemical reduction of H2PtCl6 solution to -60 °C and demonstrated such a method as a fast and convenient process for the synthesis of atomically dispersed Pt. We showed that the ultralow-temperature reaction efficiently inhibited the nucleation process by controlling its thermodynamics and kinetics. Compared with commercial platinum/carbon, the synthesized atomically dispersed Pt catalyst, as a superior HER catalyst, exhibited a lower overpotential of approximately 55 mV at a current density of 100 mA cm-2 and a lower Tafel slope of 26 mV dec-1 and had higher stability in 0.5 M H2SO4.

Room temperature Mg reduction of TiO2: formation mechanism and application in photocatalysis.

Defects in metal oxides can significantly improve their physical and chemical properties. However, the conventional methods to generate defects often require complex procedures and harsh conditions. In this study, we design a simple and room-temperature preparation route to prepare defective metal oxide nanoparticles with high yield. The formation of defects is attributed to the generation of oxygen vacancies (VO) and hydrogenation caused by charge transfer at a Mg-metal oxide junction structure. Defective TiO2 exhibits excellent performance toward wastewater cleaning and water splitting. The proposed route is promising in terms of convenience, low cost, and large-scale production.

Ultra-low-temperature growth of CdS quantum dots on g-C3N4 nanosheets and their photocatalytic performance.

CdS quantum dots deposited on carbon nitride (g-C3N4) nanosheets have been synthesized by ultra-low temperature (-60 °C) liquid phase precipitation reactions. The obtained CdS quantum dots were uniformly distributed on the surface of the g-C3N4 nanosheets with an average diameter of 5 nm. Correspondingly, CdS/g-C3N4 exhibits a highly enhanced photocatalytic performance.

Iced photochemical reduction to synthesize atomically dispersed metals by suppressing nanocrystal growth.

Photochemical solution-phase reactions have been widely applied for the syntheses of nanocrystals. In particular, tuning of the nucleation and growth of solids has been a major area of focus. Here we demonstrate a facile approach to generate atomically dispersed platinum via photochemical reduction of frozen chloroplatinic acid solution using ultraviolet light. Using this iced-photochemical reduction, the aggregation of atoms is prevented, and single atoms are successfully stabilized. The platinum atoms are deposited on various substrates, including mesoporous carbon, graphene, carbon nanotubes, titanium dioxide nanoparticles, and zinc oxide nanowires. The atomically dispersed platinum on mesoporous carbon exhibits efficient catalytic activity for the electrochemical hydrogen evolution reaction, with an overpotential of only 65 mV at a current density of 100 mA cm-2 and long-time durability (>10 h), superior to state-of-the-art platinum/carbon. This iced-photochemical reduction may be extended to other single atoms, for example gold and silver, as demonstrated in this study.

Enhanced Electrocatalytic Activity for Water Splitting on NiO/Ni/Carbon Fiber Paper.

Large-scale growth of low-cost, efficient, and durable non-noble metal-based electrocatalysts for water splitting is crucial for future renewable energy systems. Atomic layer deposition (ALD) provides a promising route for depositing uniform thin coatings of electrocatalysts, which are useful in many technologies, including the splitting of water. In this communication, we report the growth of a NiO/Ni catalyst directly on carbon fiber paper by atomic layer deposition and report subsequent reduction and oxidation annealing treatments. The 10-20 nm NiO/Ni nanoparticle catalysts can reach a current density of 10 mA·cm-2 at an overpotential of 189 mV for hydrogen evolution reactions and 257 mV for oxygen evolution reactions with high stability. We further successfully achieved a water splitting current density of 10 mA·cm-2 at 1.78 V using a typical NiO/Ni coated carbon fiber paper two-electrode setup. The results suggest that nanoparticulate NiO/Ni is an active, stable, and noble-metal-free electrocatalyst, which facilitates a method for future water splitting applications.