Synthesis and Characterization of Single-Phase Metal Dodecaboride Solid Solutions: Zr1–xYxB12 and Zr1–xUxB12

Single-phase metal dodecaboride solid solutions, Zr0.5Y0.5B12 and Zr0.5U0.5B12, were prepared by arc melting from pure elements. The phase purity and composition were established by powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), and 10B and 11B solid-state nuclear magnetic resonance (NMR) spectroscopy. The effects of carbon addition to Zr1–xYxB12 were studied and it was found that carbon causes fast cooling and as a result rapid nucleation of grains, as well as “templating” and patterning effects of the surface morphology. The hardness of the Zr0.5Y0.5B12 phase is 47.6 ± 1.7 GPa at 0.49 N load, which is ∼17% higher than that of its parent compounds, ZrB12 and YB12, with hardness values of 41.6 ± 2.6 and 37.5 ± 4.3 GPa, respectively. The hardness of Zr0.5U0.5B12 is ∼54% higher than that of its UB12 parent. The dodecaborides were confirmed to be metallic by band structure calculations, diffuse reflectance UV–vis, and solid-state NMR spectroscopies. The nature of the dodecaboride colors—violet for ZrB12 and blue for YB12—can be attributed to charge-transfer. XPS indicates that the metals are in the following oxidation states: Y3+, Zr4+, and U5+/6+. The superconducting transition temperatures (Tc) of the dodecaborides were determined to be 4.5 and 6.0 K for YB12 and ZrB12, respectively, as shown by resistivity and superconducting quantum interference device (SQUID) measurements. The Tc of the Zr0.5Y0.5B12 solid solution was suppressed to 2.5 K

Nanowire photochemical diodes for artificial photosynthesis

Artificial photosynthesis can provide a solution to our current energy needs by converting small molecules such as water or carbon dioxide into useful fuels. This can be accomplished using photochemical diodes, which interface two complementary light absorbers with suitable electrocatalysts. Nanowire semiconductors provide unique advantages in terms of light absorption and catalytic activity, yet great control is required to integrate them for overall fuel production. In this review, we journey across the progress in nanowire photoelectrochemistry (PEC) over the past two decades, revealing design principles to build these nanowire photochemical diodes. To this end, we discuss the latest progress in terms of nanowire photoelectrodes, focusing on the interplay between performance, photovoltage, electronic band structure, and catalysis. Emphasis is placed on the overall system integration and semiconductor-catalyst interface, which applies to inorganic, organic, or biologic catalysts. Last, we highlight further directions that may improve the scope of nanowire PEC systems

Photochemical Diodes for Simultaneous Bias-Free Glycerol Valorization and Hydrogen Evolution

Artificial photosynthesis offers a route to producing clean fuel energy. However, the large thermodynamic requirement for water splitting along with the corresponding sluggish kinetics for the oxygen evolution reaction (OER) limits its current practical application. Here, we offer an alternative approach by replacing the OER with the glycerol oxidation reaction (GOR) for value-added chemicals. By using a Si photoanode, a low GOR onset potential of -0.05 V vs RHE and a photocurrent density of 10 mA/cm2 at 0.5 V vs RHE can be reached. Coupled with a Si nanowire photocathode for the hydrogen evolution reaction (HER), the integrated system yields a high photocurrent density of 6 mA/cm2 with no applied bias under 1 sun illumination and can run for over 4 days under diurnal illumination. The demonstration of the GOR-HER integrated system provides a framework for designing bias-free photoelectrochemical devices at appreciable currents and establishes a facile approach to artificial photosynthesis

Synthesis of Carbohydrates from Methanol Using Electrochemical Partial Oxidation over Palladium with the Integrated Formose Reaction

Electrochemically derived multicarbon products are a golden target for valorization of captured carbon dioxide due to the potential of turning a waste product into useful commodity chemicals with renewable energy sources. As a tantalizing approach toward their synthesis, the formose reaction utilizes catalytic condensation of formaldehyde to generate carbohydrates. While a sustainable approach to artificial carbohydrate production through electrochemical generation of formaldehyde is desirable, to date, it has not been fully realized. Here, we study the electrocatalytic conversion of methanol to formaldehyde on palladium with faradaic efficiency of over 90% at 0.9 V vs Ag/AgCl and with the partial current density of nearly 3 mA cm-2 at 1.6 V vs Ag/AgCl. We observe the concurrent generation of palladium oxides as a consequence of the high overpotentials employed, which may partially explain the higher selectivity toward the partial oxidation product. Moreover, we demonstrate that formaldehyde produced electrochemically from methanol is feasible for formose reactions without the need for further purification, achieving 21-28% carbon conversion to carbohydrates. This process, therefore, represents a potential avenue for the electrochemical generation of formaldehyde and its utilization in generating multicarbon products inaccessible by other electrocatalytic means

High-Photovoltage Silicon Nanowire for Biological Cofactor Production

Photocathodic conversion of NAD+ to NADH cofactor is a promising platform for activating redox biological catalysts and enzymatic synthesis using renewable solar energy. However, many photocathodes suffer from low photovoltage, consequently requiring a high cathodic bias for NADH production. Here, we report an n+p-type silicon nanowire (n+p-SiNW) photocathode having a photovoltage of 435 mV to drive energy-efficient NADH production. The enhanced band bending at the n+/p interface accounts for the high photovoltage, which conduces to a benchmark onset potential [0.393 V vs the reversible hydrogen electrode (VRHE)] for SiNW-based photocathodic NADH generation. In addition, the n+p-SiNW nanomaterial exhibits a Faradaic efficiency of 84.7% and a conversion rate of 1.63 μmol h-1 cm-1 at 0.2 VRHE, which is the lowest cathodic potential to achieve the maximum productivity among SiNW-sensitized cofactor production

Synthesis of Carbohydrates from Methanol Using Electrochemical Partial Oxidation over Palladium with the Integrated Formose Reaction

Electrochemically derived multicarbon products are a golden target for valorization of captured carbon dioxide due to the potential of turning a waste product into useful commodity chemicals with renewable energy sources. As a tantalizing approach toward their synthesis, the formose reaction utilizes catalytic condensation of formaldehyde to generate carbohydrates. While a sustainable approach to artificial carbohydrate production through electrochemical generation of formaldehyde is desirable, to date, it has not been fully realized. Here, we study the electrocatalytic conversion of methanol to formaldehyde on palladium with faradaic efficiency of over 90% at 0.9 V vs Ag/AgCl and with the partial current density of nearly 3 mA cm–2 at 1.6 V vs Ag/AgCl. We observe the concurrent generation of palladium oxides as a consequence of the high overpotentials employed, which may partially explain the higher selectivity toward the partial oxidation product. Moreover, we demonstrate that formaldehyde produced electrochemically from methanol is feasible for formose reactions without the need for further purification, achieving 21–28% carbon conversion to carbohydrates. This process, therefore, represents a potential avenue for the electrochemical generation of formaldehyde and its utilization in generating multicarbon products inaccessible by other electrocatalytic means

Moving the Plasmon of LaB6 from IR to Near-IR via Eu-Doping

Lanthanum hexaboride (LaB6) has become a material of intense interest in recent years due to its low work function, thermal stability and intriguing optical properties. LaB6 is also a semiconductor plasmonic material with the ability to support strong plasmon modes. Some of these modes uniquely stretch into the infrared, allowing the material to absorb around 1000 nm, which is of great interest to the window industry. It is well known that the plasmon of LaB6 can be tuned by controlling particle size and shape. In this work, we explore the options available to further tune the optical properties by describing how metal vacancies and Eu doping concentrations are additional knobs for tuning the absorbance from the near-IR to far-IR in La1−xEuxB6 (x = 0, 0.2, 0.5, 0.8, and 1.0). We also report that there is a direct correlation between Eu concentration and metal vacancies within the Eu1−xLaxB6

Moving the Plasmon of LaB₆ from IR to Near-IR via Eu-Doping.

Lanthanum hexaboride (LaB₆) has become a material of intense interest in recent years due to its low work function, thermal stability and intriguing optical properties. LaB₆ is also a semiconductor plasmonic material with the ability to support strong plasmon modes. Some of these modes uniquely stretch into the infrared, allowing the material to absorb around 1000 nm, which is of great interest to the window industry. It is well known that the plasmon of LaB₆ can be tuned by controlling particle size and shape. In this work, we explore the options available to further tune the optical properties by describing how metal vacancies and Eu doping concentrations are additional knobs for tuning the absorbance from the near-IR to far-IR in La1-xEuxB₆ (x = 0, 0.2, 0.5, 0.8, and 1.0). We also report that there is a direct correlation between Eu concentration and metal vacancies within the Eu1-xLaxB₆

Photoelectrochemical CO2 Reduction toward Multicarbon Products with Silicon Nanowire Photocathodes Interfaced with Copper Nanoparticles.

The development of photoelectrochemical systems for converting CO2 into chemical feedstocks offers an attractive strategy for clean energy storage by directly utilizing solar energy, but selectivity and stability for these systems have thus been limited. Here, we interface silicon nanowire (SiNW) photocathodes with a copper nanoparticle (CuNP) ensemble to drive efficient photoelectrochemical CO2 conversion to multicarbon products. This integrated system enables CO2-to-C2H4 conversion with faradaic efficiency approaching 25% and partial current densities above 2.5 mA/cm2 at -0.50 V vs RHE, while the nanowire photocathodes deliver 350 mV of photovoltage under 1 sun illumination. Under 50 h of continual bias and illumination, CuNP/SiNW can sustain stable photoelectrochemical CO2 reduction. These results demonstrate the nanowire/catalyst system as a powerful modular platform to achieve stable photoelectrochemical CO2 reduction and the feasibility to facilitate complex reactions toward multicarbons using generated photocarriers