Solution Synthesis of Thiospinel CuCo2S4 Nanoparticles.

CuCo2S4 is an important mixed-metal spinel-type sulfide that is typically synthesized using high-temperature solid-state reactions, which produce agglomerated particles with low surface areas that are not optimal for applications such as heterogeneous catalysis. Here, we show that highly crystalline and nonagglomerated colloidal CuCo2S4 nanoparticles can be synthesized in solution at 200 °C, which is significantly lower than previously reported methods. The CuCo2S4 nanoparticles were found to be highly active electrocatalysts for the oxygen evolution reaction (OER) under strongly alkaline conditions (1.0 M KOH, pH 14), requiring an OER overpotential of 395 mV to produce a current density of 10 mA cm(-2). X-ray photoelectron spectroscopy (XPS) studies showed evidence of oxide formation, suggesting, in conjunction with the observed electrocatalytic properties, that the mixed-metal sulfides may serve as precursors to oxides and/or hydroxides, which are likely to be the catalytically active species.

Low-Temperature Solution Synthesis of Few-Layer 1T '-MoTe2 Nanostructures Exhibiting Lattice Compression.

Molybdenum ditelluride, MoTe2 , is emerging as an important transition-metal dichalcogenide (TMD) material because of its favorable properties relative to other TMDs. The 1T ' polymorph of MoTe2 is particularly interesting because it is semimetallic with bands that overlap near the Fermi level, but semiconducting 2H-MoTe2 is more stable and therefore more accessible synthetically. Metastable 1T '-MoTe2 forms directly in solution at 300 °C as uniform colloidal nanostructures that consist of few-layer nanosheets, which appear to exhibit an approx. 1 % lateral lattice compression relative to the bulk analogue. Density functional theory calculations suggest that small grain sizes and polycrystallinity stabilize the 1T ' phase in the MoTe2 nanostructures and suppress its transformation back to the more stable 2H polymorph through grain boundary pinning. Raman spectra of the 1T '-MoTe2 nanostructures exhibit a laser energy dependence, which could be caused by electronic transitions.

Colloidal Hybrid Nanoparticle Insertion Reaction for Transforming Heterodimers into Heterotrimers.

Three-component colloidal hybrid nanoparticles, which are central to a diverse array of applications, are typically synthesized using successive seeded growth steps, which are additive in nature and driven by surface chemistry considerations and material-specific preferences for nucleation and growth. Here, we describe a new nanoparticle insertion reaction for transforming heterodimers into heterotrimers, which is based on a supersaturation-precipitation pathway that shifts the driving force for heterotrimer formation away from surface-driven nucleation and growth. To demonstrate the concept, a Ge segment is inserted between the Au and Fe3O4 domains of Au-Fe3O4 heterodimers to form Au-Ge-Fe3O4 heterotrimers. Microscopic investigations reveal important mechanistic insights, including identification of a proposed Au-Ge-Au-Fe3O4 intermediate. The process can be modified to access the analogous addition product Ge-Au-Fe3O4, allowing tuning between two distinct heterotrimer isomers with different configurations.

Sequential Anion and Cation Exchange Reactions for Complete Material Transformations of Nanoparticles with Morphological Retention.

Ion exchange reactions of colloidal nanocrystals provide access to complex products that are synthetically challenging using traditional hot-injection methods. However, such reactions typically achieve only partial material transformations by employing either cation or anion exchange processes. It is now shown that anion and cation exchange reactions can be coupled together and applied sequentially in one integrated pathway that leads to complete material transformations of nanocrystal templates. Although the product nanocrystals do not contain any of the original constituent elements, the original morphology is retained, thereby fully decoupling morphology and composition control. The sequential anion/cation exchange process was applied to pseudo-spherical CdO nanocrystals and ZnO tetrapods, producing fully transformed and shape-controlled nanocrystals of copper and silver sulfides and selenides. Furthermore, hollow core-shell tetrapod ZnS@CdS heterostructures were readily accessible.

Highly active electrocatalysis of the hydrogen evolution reaction by cobalt phosphide nanoparticles.

Nanoparticles of cobalt phosphide, CoP, have been prepared and evaluated as electrocatalysts for the hydrogen evolution reaction (HER) under strongly acidic conditions (0.50 M H2SO4, pH 0.3). Uniform, multi-faceted CoP nanoparticles were synthesized by reacting Co nanoparticles with trioctylphosphine. Electrodes comprised of CoP nanoparticles on a Ti support (2 mg cm(-2) mass loading) produced a cathodic current density of 20 mA cm(-2) at an overpotential of -85 mV. The CoP/Ti electrodes were stable over 24 h of sustained hydrogen production in 0.50 M H2SO4. The activity was essentially unchanged after 400 cyclic voltammetric sweeps, suggesting long-term viability under operating conditions. CoP is therefore amongst the most active, acid-stable, earth-abundant HER electrocatalysts reported to date.

Nanostructured nickel phosphide as an electrocatalyst for the hydrogen evolution reaction.

Nanoparticles of nickel phosphide (Ni2P) have been investigated for electrocatalytic activity and stability for the hydrogen evolution reaction (HER) in acidic solutions, under which proton exchange membrane-based electrolysis is operational. The catalytically active Ni2P nanoparticles were hollow and faceted to expose a high density of the Ni2P(001) surface, which has previously been predicted based on theory to be an active HER catalyst. The Ni2P nanoparticles had among the highest HER activity of any non-noble metal electrocatalyst reported to date, producing H2(g) with nearly quantitative faradaic yield, while also affording stability in aqueous acidic media.

Enhancing the activity of oxygen-evolution and chlorine-evolution electrocatalysts by atomic layer deposition of TiO2.

We report that TiO2 coatings formed via atomic layer deposition (ALD) may tune the activity of IrO2, RuO2, and FTO for the oxygen-evolution and chlorine-evolution reactions (OER and CER). Electrocatalysts exposed to ~3-30 ALD cycles of TiO2 exhibited overpotentials at 10 mA cm-2 of geometric current density that were several hundred millivolts lower than uncoated catalysts, with correspondingly higher specific activities. For example, the deposition of TiO2 onto IrO2 yielded a 9-fold increase in the OER-specific activity in 1.0 M H2SO4 (0.1 to 0.9 mA cmECSA -2 at 350 mV overpotential). The oxidation state of titanium and the potential of zero charge were also a function of the number of ALD cycles, indicating a correlation between oxidation state, potential of zero charge, and activity of the tuned electrocatalysts.

General Strategy for the Synthesis of Transition Metal Phosphide Films for Electrocatalytic Hydrogen and Oxygen Evolution.

Transition metal phosphides recently have been identified as promising Earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER). Here, we present a general and scalable strategy for the synthesis of transition metal phosphide electrodes based on the reaction of commercially available metal foils (Fe, Co, Ni, Cu, and NiFe) with various organophosphine reagents. The resulting phosphide electrodes were found to exhibit excellent electrocatalytic HER and OER performance. The most active electrodes required overpotentials of only -128 mV for the HER in acid (Ni2P), -183 mV for the HER in base (Ni2P), and 277 mV for the OER in base (NiFeP) to produce operationally relevant current densities of 10 mA cm(-2). Such HER and OER performance compares favorably with samples prepared using significantly more elaborate and costly procedures. Furthermore, we demonstrate that the approach can also be utilized to obtain highly active and conformal metal phosphide coatings on photocathode materials, such as highly doped Si, that are relevant to solar fuels production.

Comparison of the Performance of CoP-Coated and Pt-Coated Radial Junction n(+)p-Silicon Microwire-Array Photocathodes for the Sunlight-Driven Reduction of Water to H2(g).

The electrocatalytic performance for hydrogen evolution has been evaluated for radial-junction n(+)p-Si microwire (MW) arrays with Pt or cobalt phosphide, CoP, nanoparticulate catalysts in contact with 0.50 M H2SO4(aq). The CoP-coated (2.0 mg cm(-2)) n(+)p-Si MW photocathodes were stable for over 12 h of continuous operation and produced an open-circuit photovoltage (Voc) of 0.48 V, a light-limited photocurrent density (Jph) of 17 mA cm(-2), a fill factor (ff) of 0.24, and an ideal regenerative cell efficiency (ηIRC) of 1.9% under simulated 1 Sun illumination. Pt-coated (0.5 mg cm(-2)) n(+)p-Si MW-array photocathodes produced Voc = 0.44 V, Jph = 14 mA cm(-2), ff = 0.46, and η = 2.9% under identical conditions. Thus, the MW geometry allows the fabrication of photocathodes entirely comprised of earth-abundant materials that exhibit performance comparable to that of devices that contain Pt.

Electrocatalytic hydrogen evolution using amorphous tungsten phosphide nanoparticles.

Amorphous tungsten phosphide (WP), which has been synthesized as colloidal nanoparticles with an average diameter of 3 nm, has been identified as a new electrocatalyst for the hydrogen-evolution reaction (HER) in acidic aqueous solutions. WP/Ti electrodes produced current densities of -10 mA cm(-2) and -20 mA cm(-2) at overpotentials of only -120 mV and -140 mV, respectively, in 0.50 M H2SO4(aq).

Electrocatalytic and photocatalytic hydrogen production from acidic and neutral-pH aqueous solutions using iron phosphide nanoparticles.

Nanostructured transition-metal phosphides have recently emerged as Earth-abundant alternatives to platinum for catalyzing the hydrogen-evolution reaction (HER), which is central to several clean energy technologies because it produces molecular hydrogen through the electrochemical reduction of water. Iron-based catalysts are very attractive targets because iron is the most abundant and least expensive transition metal. We report herein that iron phosphide (FeP), synthesized as nanoparticles having a uniform, hollow morphology, exhibits among the highest HER activities reported to date in both acidic and neutral-pH aqueous solutions. As an electrocatalyst operating at a current density of -10 mA cm(-2), FeP nanoparticles deposited at a mass loading of ∼1 mg cm(-2) on Ti substrates exhibited overpotentials of -50 mV in 0.50 M H2SO4 and -102 mV in 1.0 M phosphate buffered saline. The FeP nanoparticles supported sustained hydrogen production with essentially quantitative faradaic yields for extended time periods under galvanostatic control. Under UV illumination in both acidic and neutral-pH solutions, FeP nanoparticles deposited on TiO2 produced H2 at rates and amounts that begin to approach those of Pt/TiO2. FeP therefore is a highly Earth-abundant material for efficiently facilitating the HER both electrocatalytically and photocatalytically.