Primary Corrosion Processes for Polymer-Embedded Free-Standing or Substrate-Supported Silicon Microwire Arrays in Aqueous Alkaline Electrolytes.

Solar fuel devices have shown promise as a sustainable source of chemical fuels. However, long-term stability of light absorbing materials remains a substantial barrier to practical devices. Herein, multiple corrosion pathways in 1 M KOH(aq) have been defined for TiO2-protected Si microwire arrays in a polymer membrane either attached to a substrate or free-standing. Top-down corrosion was observed in both morphologies through defects in the TiO2 coating. For the substrate-based samples, bottom-up corrosion was observed through the substrate and up the adjacent wires. In the free-standing samples, uniform bottom-up corrosion was observed through the membrane with all wire material corroded within 10 days of immersion in the dark in 1 M KOH(aq).

Defect-Seeded Atomic Layer Deposition of Metal Oxides on the Basal Plane of 2D Layered Materials.

Atomic layer deposition (ALD) on mechanically exfoliated 2D layered materials spontaneously produces network patterns of metal oxide nanoparticles in triangular and linear deposits on the basal surface. The network patterns formed under a range of ALD conditions and were independent of the orientation of the substrate in the ALD reactor. The patterns were produced on MoS2 or HOPG when either tetrakis(dimethylamido)titanium or bis(ethylcyclopentadienyl)manganese were used as precursors, suggesting that the phenomenon is general for 2D materials. Transmission electron microscopy revealed the presence, prior to deposition, of dislocation networks along the basal plane of mechanically exfoliated 2D flakes, indicating that periodical basal plane defects related to disruptions in the van der Waals stacking of layers, such as perfect line dislocations and triangular extended stacking faults networks, introduce a surface reactivity landscape that leads to the emergence of patterned deposition.

Efficient hydrogen evolution catalysis using ternary pyrite-type cobalt phosphosulphide.

The scalable and sustainable production of hydrogen fuel through water splitting demands efficient and robust Earth-abundant catalysts for the hydrogen evolution reaction (HER). Building on promising metal compounds with high HER catalytic activity, such as pyrite structure cobalt disulphide (CoS2), and substituting non-metal elements to tune the hydrogen adsorption free energy could lead to further improvements in catalytic activity. Here we present a combined theoretical and experimental study to establish ternary pyrite-type cobalt phosphosulphide (CoPS) as a high-performance Earth-abundant catalyst for electrochemical and photoelectrochemical hydrogen production. Nanostructured CoPS electrodes achieved a geometrical catalytic current density of 10 mA cm(-2) at overpotentials as low as 48 mV, with outstanding long-term operational stability. Integrated photocathodes of CoPS on n(+)-p-p(+) silicon micropyramids achieved photocurrents up to 35 mA cm(-2) at 0 V versus the reversible hydrogen electrode (RHE), onset photovoltages as high as 450 mV versus RHE, and the most efficient solar-driven hydrogen generation from Earth-abundant systems.

Hydrothermal continuous flow synthesis and exfoliation of NiCo layered double hydroxide nanosheets for enhanced oxygen evolution catalysis.

We report the controlled synthesis of NiCo layered double hydroxide (LDH) nanoplates using a newly developed high temperature high pressure hydrothermal continuous flow reactor (HCFR), which enables direct growth onto conductive substrates in high yield and, most importantly, better control of the precursor supersaturation and, thus, nanostructure morphology and size. The solution coordination chemistry of metal-ammonia complexes was utilized to synthesize well-defined NiCo LDH nanoplates directly in a single step without topochemical oxidation. The as-grown NiCo LDH nanoplates exhibit a high catalytic activity toward the oxygen evolution reaction (OER). By chemically exfoliating LDH nanoplates to thinner nanosheets, the catalytic activity can be further enhanced to yield an electrocatalytic current density of 10 mA cm(-2) at an overpotential of 367 mV and a Tafel slope of 40 mV dec(-1). Such enhancement could be due to the increased surface area and more exposed active sites. X-ray photoelectron spectroscopy (XPS) suggests the exfoliation also caused some changes in electronic structure. This work presents general strategies to controllably grow nanostructures of LDH and ternary oxide/hydroxides in general and to enhance the electrocatalytic performance of layered nanostructures by exfoliation.

Integrated Photoelectrochemical Solar Energy Conversion and Organic Redox Flow Battery Devices.

Building on regenerative photoelectrochemical solar cells and emerging electrochemical redox flow batteries (RFBs), more efficient, scalable, compact, and cost-effective hybrid energy conversion and storage devices could be realized. An integrated photoelectrochemical solar energy conversion and electrochemical storage device is developed by integrating regenerative silicon solar cells and 9,10-anthraquinone-2,7-disulfonic acid (AQDS)/1,2-benzoquinone-3,5-disulfonic acid (BQDS) RFBs. The device can be directly charged by solar light without external bias, and discharged like normal RFBs with an energy storage density of 1.15 Wh L-1 and a solar-to-output electricity efficiency (SOEE) of 1.7 % over many cycles. The concept exploits a previously undeveloped design connecting two major energy technologies and promises a general approach for storing solar energy electrochemically with high theoretical storage capacity and efficiency.

Gated Hall effect of nanoplate devices reveals surface-state-induced surface inversion in iron pyrite semiconductor.

Understanding semiconductor surface states is critical for their applications, but fully characterizing surface electrical properties is challenging. Such a challenge is especially crippling for semiconducting iron pyrite (FeS2), whose potential for solar energy conversion has been suggested to be held back by rich surface states. Here, by taking advantage of the high surface-to-bulk ratio in nanostructures and effective electrolyte gating, we develop a general method to fully characterize both the surface inversion and bulk electrical transport properties for the first time through electrolyte-gated Hall measurements of pyrite nanoplate devices. Our study shows that pyrite is n-type in the bulk and p-type near the surface due to strong inversion and yields the concentrations and mobilities of both bulk electrons and surface holes. Further, solutions of the Poisson equation reveal a high-density of surface holes accumulated in a 1.3 nm thick strong inversion layer and an upward band bending of 0.9-1.0 eV. This work presents a general methodology for using transport measurements of nanostructures to study both bulk and surface transport properties of semiconductors. It also suggests that high-density of surface states are present on surface of pyrite, which partially explains the universal p-type conductivity and lack of photovoltage in polycrystalline pyrite.

Efficient photoelectrochemical hydrogen generation using heterostructures of Si and chemically exfoliated metallic MoS2.

We report the preparation and characterization of highly efficient and robust photocathodes based on heterostructures of chemically exfoliated metallic 1T-MoS2 and planar p-type Si for solar-driven hydrogen production. Photocurrents up to 17.6 mA/cm(2) at 0 V vs reversible hydrogen electrode were achieved under simulated 1 sun irradiation, and excellent stability was demonstrated over long-term operation. Electrochemical impedance spectroscopy revealed low charge-transfer resistances at the semiconductor/catalyst and catalyst/electrolyte interfaces, and surface photoresponse measurements also demonstrated slow carrier recombination dynamics and consequently efficient charge carrier separation, providing further evidence for the superior performance. Our results suggest that chemically exfoliated 1T-MoS2/Si heterostructures are promising earth-abundant alternatives to photocathodes based on noble metal catalysts for solar-driven hydrogen production.

Ionization of high-density deep donor defect states explains the low photovoltage of iron pyrite single crystals.

Iron pyrite (FeS2) is considered a promising earth-abundant semiconductor for solar energy conversion with the potential to achieve terawatt-scale deployment. However, despite extensive efforts and progress, the solar conversion efficiency of iron pyrite remains below 3%, primarily due to a low open circuit voltage (VOC). Here we report a comprehensive investigation on {100}-faceted n-type iron pyrite single crystals to understand its puzzling low VOC. We utilized electrical transport, optical spectroscopy, surface photovoltage, photoelectrochemical measurements in aqueous and acetonitrile electrolytes, UV and X-ray photoelectron spectroscopy, and Kelvin force microscopy to characterize the bulk and surface defect states and their influence on the semiconducting properties and solar conversion efficiency of iron pyrite single crystals. These insights were used to develop a circuit model analysis for the electrochemical impedance spectroscopy that allowed a complete characterization of the bulk and surface defect states and the construction of a detailed energy band diagram for iron pyrite crystals. A holistic evaluation revealed that the high-density of intrinsic surface states cannot satisfactorily explain the low photovoltage; instead, the ionization of high-density bulk deep donor states, likely resulting from bulk sulfur vacancies, creates a nonconstant charge distribution and a very narrow surface space charge region that limits the total barrier height, thus satisfactorily explaining the limited photovoltage and poor photoconversion efficiency of iron pyrite single crystals. These findings lead to suggestions to improve single crystal pyrite and nanocrystalline or polycrystalline pyrite films for successful solar applications.

Synthesis and properties of semiconducting iron pyrite (FeS2) nanowires.

We report the growth and structural, electrical, and optical characterization of vertically oriented single-crystalline iron pyrite (FeS(2)) nanowires synthesized via thermal sulfidation of steel foil for the first time. The pyrite nanowires have diameters of 4-10 nm and lengths greater than 2 µm. Their crystal phase was identified as cubic iron pyrite using high-resolution transmission electron microscopy, Raman spectroscopy, and powder X-ray diffraction. Electrical transport measurements showed the pyrite nanowires to be highly p-doped, with an average resistivity of 0.18 ± 0.09 Ω cm and carrier concentrations on the order of 10(21) cm(-3). These pyrite nanowires could provide a platform to further study and improve the physical properties of pyrite nanostructures toward solar energy conversion.

Selective-Area, Water-Free Atomic Layer Deposition of Metal Oxides on Graphene Defects.

Passivating defective regions on monolayer graphene with metal oxides remains an active area of research for graphene device integration. To effectively passivate these regions, a water-free atomic layer deposition (ALD) recipe was developed and yielded selective-area ALD (sa-ALD) of mixed-metal oxides onto line defects in monolayer graphene. The anisotropically deposited film targeted high-energy defect sites that were formed during synthesis or transfer of the graphene layer. The passivating layer exceeded 10 nm thickness with minimal deposition onto the basal plane of graphene. The mixed-metal oxide film was of comparable quality to films deposited using nonselective water-based ALD methods, as shown by X-ray photoelectron spectroscopy. The development of sa-ALD techniques to target defect regions on the graphene sheet, while keeping the basal plane intact, will provide a new mechanism to passivate graphene defects and modify the electronic and physical properties of graphene.

Metal organic framework-derived CoPS/N-doped carbon for efficient electrocatalytic hydrogen evolution.

Electrocatalytic hydrogen evolution has attracted a great deal of attention due to the urgent need for clean energy. Herein, we demonstrate the synthesis of ternary pyrite-type cobalt phosphosulphide (CoPS) nanoparticles supported on a nitrogen-doped carbon matrix, CoPS/N-C, through carbonization and subsequent phosphosulfurization of Co-based zeolitic imidazolate frameworks (ZIF-67), as promising hydrogen evolution reaction (HER) electrocatalysts in both acidic and alkaline solutions. The polyhedral structure of ZIF-67 can be well maintained in the as-prepared CoPS/N-C nanocomposites. In particular, CoPS/N-C provides a geometric catalytic current density of -10 mA cm-2 at overpotentials of -80 and -148 mV vs. a reversible hydrogen electrode (RHE) and a Tafel slope of 68 and 78 mV dec-1 in 0.5 M H2SO4 and 1 M KOH, respectively, which is superior to most of the transition metal phosphosulfide materials. This MOF-derived synthesis of a transition metal phosphosulfide supported heteroatom-doped carbon matrix provides a promising opportunity for the development of highly efficient electrocatalysts for renewable energy devices.

Designing Efficient Solar-Driven Hydrogen Evolution Photocathodes Using Semitransparent MoQxCly (Q = S, Se) Catalysts on Si Micropyramids.

Silicon micropyramids with n(+) pp(+) junctions are demonstrated to be efficient absorbers for integrated solar-driven hydrogen production systems enabling significant improvements in both photocurrent and onset potential. When conformally coated with MoSx Cly , a catalyst that has excellent catalytic activity and high optical transparency, the highest photocurrent density for Si-based photocathodes with earth-abundant catalysts is achieved.

High-purity iron pyrite (FeS2) nanowires as high-capacity nanostructured cathodes for lithium-ion batteries.

Iron pyrite is an earth-abundant and inexpensive material that has long been interesting for electrochemical energy storage and solar energy conversion. A large-scale conversion synthesis of phase-pure pyrite nanowires has been developed for the first time. Nano-pyrite cathodes exhibited high Li-storage capacity and excellent capacity retention in Li/pyrite batteries using a liquid electrolyte, which retained a discharge capacity of 350 mAh g(-1) and a discharge energy density of 534 Wh kg(-1) after 50 cycles at 0.1 C rate.

Earth-Abundant Cobalt Pyrite (CoS2) Thin Film on Glass as a Robust, High-Performance Counter Electrode for Quantum Dot-Sensitized Solar Cells.

We report a cobalt pyrite (cobalt disulfide, CoS2) thin film on glass as a robust, high-performance, low-cost, earth-abundant counter electrode for liquid-junction quantum dot-sensitized solar cells (QDSSCs) that employ the aqueous sulfide/polysulfide (S(2-)/Sn(2-)) redox electrolyte as the hole-transporting medium. The metallic CoS2 thin film electrode is prepared via thermal sulfidation of a cobalt film deposited on glass and has been characterized by powder X-ray diffraction and electron microscopy. Using the CoS2 counter electrode, CdS/CdSe-sensitized QDSSCs display improved short-circuit photocurrent density and fill factor, achieving solar light-to-electricity conversion efficiencies as high as 4.16%, with an average efficiency improvement of 54 (±14)% over equivalent devices assembled with a traditional platinum counter electrode. Electrochemical measurements verify that CoS2 shows high electrocatalytic activity toward polysulfide reduction, rationalizing the improved QDSSC performance. CoS2 is also less susceptible to poisoning by the sulfide/polysulfide electrolyte, a problem that plagues platinum electrodes in this application; furthermore, CoS2 exhibits excellent stability in sulfide/polysulfide electrolyte, resulting in highly reproducible performance.

Synthesis, characterization, and variable range hopping transport of pyrite (FeS2) nanorods, nanobelts, and nanoplates.

We report the growth, structural, and electrical characterization of single-crystalline iron pyrite (FeS2) nanorods, nanobelts, and nanoplates synthesized via sulfidation reaction with iron dichloride (FeCl2) and iron dibromide (FeBr2). The as-synthesized products were confirmed to be single-crystal phase pure cubic iron pyrite using powder X-ray diffraction, Raman spectroscopy, and transmission electron microscopy. An intermediate reaction temperature of 425 °C or a high sulfur vapor pressure under high temperatures was found to be critical for the formation of phase pure pyrite. Field effect transport measurements showed that these pyrite nanostructures appear to behave as a moderately p-doped semiconductor with an average resistivity of 2.19 ± 1.21 Ω·cm, an improved hole mobility of 0.2 cm² V⁻¹ s⁻¹, and a lower carrier concentration on the order of 10¹8-10¹9 cm⁻³ compared with previous reported pyrite nanowires. Temperature-dependent electrical transport measurements reveal Mott variable range hopping transport in the temperature range 40-220 K and transport via thermal activation of carriers with an activation energy of 100 meV above room temperature (300-400 K). Most importantly, the transport properties of the pyrite nanodevices do not change if highly pure (99.999%) precursors are utilized, suggesting that the electrical transport is dominated by intrinsic defects in pyrite. These single-crystal pyrite nanostructures are nice platforms to further study the carrier conduction mechanisms, semiconductor defect physics, and surface properties in depth, toward improving the physical properties of pyrite for efficient solar energy conversion.