Bimetallic Metal Sites in Metal-Organic Frameworks Facilitate the Production of 1-Butene from Electrosynthesized Ethylene.

Converting CO2 to synthetic hydrocarbon fuels is of increasing interest. In light of progress in electrified CO2 to ethylene, we explored routes to dimerize to 1-butene, an olefin that can serve as a building block to ethylene longer-chain alkanes. With goal of selective and active dimerization, we investigate a series of metal-organic frameworks having bimetallic catalytic sites. We find that the tunable pore structure enables optimization of selectivity and that periodic pore channels enhance activity. In a tandem system for the conversion of CO2 to 1-C4H8, wherein the outlet cathodic gas from a CO2-to-C2H4 electrolyzer is fed directly (via a dehumidification stage) into the C2H4 dimerizer, we study the highest-performing MOF found herein: M' = Ru and M″ = Ni in the bimetallic two-dimensional M'2(OAc)4M″(CN)4 MOF. We report a 1-C4H8 production rate of 1.3 mol gcat-1 h-1 and a C2H4 conversion of 97%. From these experimental data, we project an estimated cradle-to-gate carbon intensity of -2.1 kg-CO2e/kg-1-C4H8 when CO2 is supplied from direct air capture and when the required energy is supplied by electricity having the carbon intensity of wind.

Selective Electrified Propylene-to-Propylene Glycol Oxidation on Activated Rh-Doped Pd.

Renewable-energy-powered electrosynthesis has the potential to contribute to decarbonizing the production of propylene glycol, a chemical that is used currently in the manufacture of polyesters and antifreeze and has a high carbon intensity. Unfortunately, to date, the electrooxidation of propylene under ambient conditions has suffered from a wide product distribution, leading to a low faradic efficiency toward the desired propylene glycol. We undertook mechanistic investigations and found that the reconstruction of Pd to PdO occurs, followed by hydroxide formation under anodic bias. The formation of this metastable hydroxide layer arrests the progressive dissolution of Pd in a locally acidic environment, increases the activity, and steers the reaction pathway toward propylene glycol. Rh-doped Pd further improves propylene glycol selectivity. Density functional theory (DFT) suggests that the Rh dopant lowers the energy associated with the production of the final intermediate in propylene glycol formation and renders the desorption step spontaneous, a concept consistent with experimental studies. We report a 75% faradic efficiency toward propylene glycol maintained over 100 h of operation.

Regulating the surface of anion-doped TiO2 nanorods by hydrogen annealing for superior photoelectrochemical water oxidation.

Dedications to achieve the highly efficient metal oxide semiconductor for the photoelectrochemical water splitting system have been persisted to utilize the TiO2 as the promising photoanode material. Herein, we report notable progress for nanostructured TiO2 photoanodes using facile sequential one-pot hydrothermal synthesis and annealing in hydrogen. A photocurrent density of 3.04 mA·cm-2 at 1.23 V vs. reversible hydrogen electrode was achieved in TiO2 nanorod arrays annealed in hydrogen ambient, which is approximately 4.25 times higher than that of pristine TiO2 annealed in ambient air. 79.2% of incident photon-to-current efficiency at 380 nm wavelength demonstrates the prominence of the material at the near-UV spectral range region and 100 h chronoamperometric test exhibits the stability of the photoanode. Detailed studies regarding crystallinity, bandgap, and elemental analysis provide the importance of the optimized annealing condition for the TiO2-based photoanodes. Water contact angle measurement displays the effect of hydrogen annealing on the hydrophilicity of the material. This study clearly demonstrates the marked improvement using the optimized hydrogen annealing, providing the promising methodologies for eco-friendly mass production of water splitting photoelectrodes.

Surface-Tailored Medium Entropy Alloys as Radically Low Overpotential Oxygen Evolution Electrocatalysts.

Numerous studies have explored new materials for electrocatalysts, but it is difficult to discover materials that surpass the catalytic activity of current commercially available noble metal electrocatalysts. In contrast to conventional transition metal alloys, high-entropy alloys (HEAs) have immense potential to maximize their catalytic properties because of their high stability and compositional diversity as oxygen evolution reactions (OERs). This work presents medium-entropy alloys (MEAs) as OER electrocatalysts to simultaneously satisfy the requirement of high catalytic activity and long-term stability. The surface of MEA electrocatalyst is tailored to suit the OER via anodizing and cyclic voltammetry activation methods. Optimized electrical properties and hydrophilicity of the surface enable an extremely low overpotential of 187 mV for achieving the current density of 10 mA cm-2 alkaline media. Furthermore, a combined photovoltaic-electrochemical system with MEA electrocatalyst and a perovskite/Si tandem solar cell exhibits a solar-to-hydrogen conversion efficiency of 20.6% for an unassisted hydrogen generation system. These results present a new pathway for designing sustainable high efficiency water splitting cells.

Crystal Facet Engineering of TiO2 Nanostructures for Enhancing Photoelectrochemical Water Splitting with BiVO4 Nanodots.

Although bismuth vanadate (BiVO4) has been promising as photoanode material for photoelectrochemical water splitting, its charge recombination issue by short charge diffusion length has led to various studies about heterostructure photoanodes. As a hole blocking layer of BiVO4, titanium dioxide (TiO2) has been considered unsuitable because of its relatively positive valence band edge and low electrical conductivity. Herein, a crystal facet engineering of TiO2 nanostructures is proposed to control band structures for the hole blocking layer of BiVO4 nanodots. We design two types of TiO2 nanostructures, which are nanorods (NRs) and nanoflowers (NFs) with different (001) and (110) crystal facets, respectively, and fabricate BiVO4/TiO2 heterostructure photoanodes. The BiVO4/TiO2 NFs showed 4.8 times higher photocurrent density than the BiVO4/TiO2 NRs. Transient decay time analysis and time-resolved photoluminescence reveal the enhancement is attributed to the reduced charge recombination, which is originated from the formation of type II band alignment between BiVO4 nanodots and TiO2 NFs. This work provides not only new insights into the interplay between crystal facets and band structures but also important steps for the design of highly efficient photoelectrodes.

Grain Boundaries Boost Oxygen Evolution Reaction in NiFe Electrocatalysts.

In a polycrystalline material, the grain boundaries (GBs) can be effective active sites for catalytic reactions by providing an electrodynamically favorable surface. Previous studies have shown that grain boundary density is related to the catalytic activity of the carbon dioxide reduction reaction, but there is still no convincing evidence that the GBs provide surfaces with enhanced activity for oxygen evolution reaction (OER). Combination of various electrochemical measurements and chemical analysis reveals the GB density at surface of NiFe electrocatalysts directly affects the overall OER. In situ electrochemical microscopy vividly shows that the OER occurs mainly at the GB during overall reaction. It is observed that the reaction determining steps are altered by grain boundary densities and the meaningful work function difference between the inside of grain and GBs exists. High-resolution transmission electron microscopy shows that extremely high index planes are exposed at the GBs, enhancing the oxygen evolution activity. The specific nature of GBs and its effects on the OER demonstrated in this study can be applied to the various polycrystalline electrocatalysts.

Water Splitting Exceeding 17% Solar-to-Hydrogen Conversion Efficiency Using Solution-Processed Ni-Based Electrocatalysts and Perovskite/Si Tandem Solar Cell.

Various noble metal-free electrocatalysts have been explored to enhance the overall water splitting efficiency. Ni-based compounds have attracted substantial attention for achieving efficient oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) catalysts. Here, we show superior electrocatalysts based on NiFe alloy electroformed by a roll-to-roll process. NiFe (oxy)hydroxide synthesized by an anodization method for the OER catalyst shows an overpotential of 250 mV at 10 mA cm-2, which is dramatically smaller than that of bare NiFe alloy with an overpotential of 380 mV at 10 mA cm-2. Electrodeposited NiMo films for the HER catalyst also exhibit a small overpotential of 100 mV at 10 mA cm-2 compared with that of bare NiFe alloy (550 mV at 10 mA cm-2). A combined spectroscopic and electrochemical analysis reveals a clear relationship between the surface chemistry of NiFe (oxy)hydroxide and the water splitting properties. These outstanding fully solution-processed catalysts facilitate superb overall water splitting properties due to enlarged active surfaces and highly active catalytic properties. We combined a solution-processed monolithic perovskite/Si tandem solar cell with MAPb(I0.85Br0.15)3 for the direct conversion of solar energy into hydrogen energy, leading to the high solar-to-hydrogen efficiency of 17.52%. Based on the cost-effective solution processes, our photovoltaic-electrocatalysis (PV-EC) system has advantages over latest high-performance solar water splitting systems.

All-Solution-Processed WO3/BiVO4 Core-Shell Nanorod Arrays for Highly Stable Photoanodes.

Tungsten oxide (WO3) and bismuth vanadate (BiVO4) are one of the most attractive combinations to construct an efficient heterojunction for photoelectrochemical (PEC) applications. Here, we report an all-solution-processed WO3/BiVO4 heteronanostructure photoanode with highly enhanced photoactivity and stability for sustainable energy production. The vertically aligned WO3 nanorods were synthesized on a fluorine-doped tin oxide/glass substrate by the hydrothermal method without a seed layer and BiVO4 was deposited by pulsed electrodeposition for conformal coating. Owing to the long diffusion lengths of charge carriers in the WO3 nanorods, the ability to absorb the wider range of wavelengths, and appropriate band-edge positions of the WO3/BiVO4 heterojunction for spontaneous PEC reaction, the optimum WO3/BiVO4 photoanode has a photocurrent density of 4.15 mA/cm2 at 1.23 V versus RHE and an incident-photon-to-current efficiency of 75.9% at 430 nm under front illumination, which are a double and quadruple those of pristine WO3 nanorod arrays, respectively. Our work suggests an environment-friendly and low-cost all-solution process route to synthesize high-quality photoelectrodes.

Efficient Water Splitting Cascade Photoanodes with Ligand-Engineered MnO Cocatalysts.

The band edge positions of semiconductors determine functionality in solar water splitting. While ligand exchange is known to enable modification of the band structure, its crucial role in water splitting efficiency is not yet fully understood. Here, ligand-engineered manganese oxide cocatalyst nanoparticles (MnO NPs) on bismuth vanadate (BiVO4) anodes are first demonstrated, and a remarkably enhanced photocurrent density of 6.25 mA cm-2 is achieved. It is close to 85% of the theoretical photocurrent density (≈7.5 mA cm-2) of BiVO4. Improved photoactivity is closely related to the substantial shifts in band edge energies that originate from both the induced dipole at the ligand/MnO interface and the intrinsic dipole of the ligand. Combined spectroscopic analysis and electrochemical study reveal the clear relationship between the surface modification and the band edge positions for water oxidation. The proposed concept has considerable potential to explore new, efficient solar water splitting systems.

Dominance of Plasmonic Resonant Energy Transfer over Direct Electron Transfer in Substantially Enhanced Water Oxidation Activity of BiVO4 by Shape-Controlled Au Nanoparticles.

The performance of plasmonic Au nanostructure/metal oxide heterointerface shows great promise in enhancing photoactivity, due to its ability to confine light to the small volume inside the semiconductor and modify the interfacial electronic band structure. While the shape control of Au nanoparticles (NPs) is crucial for moderate bandgap semiconductors, because plasmonic resonance by interband excitations overlaps above the absorption edge of semiconductors, its critical role in water splitting is still not fully understood. Here, first, the plasmonic effects of shape-controlled Au NPs on bismuth vanadate (BiVO4 ) are studied, and a largely enhanced photoactivity of BiVO4 is reported by introducing the octahedral Au NPs. The octahedral Au NP/BiVO4 achieves 2.4 mA cm-2 at the 1.23 V versus reversible hydrogen electrode, which is the threefold enhancement compared to BiVO4 . It is the highest value among the previously reported plasmonic Au NPs/BiVO4 . Improved photoactivity is attributed to the localized surface plasmon resonance; direct electron transfer (DET), plasmonic resonant energy transfer (PRET). The PRET can be stressed over DET when considering the moderate bandgap semiconductor. Enhanced water oxidation induced by the shape-controlled Au NPs is applicable to moderate semiconductors, and shows a systematic study to explore new efficient plasmonic solar water splitting cells.

Enantiomeric Synthesis of L-(or 1'R,2'S)-Carbocyclic Cyclopropyl Nucleosides.

The enantiomeric synthesis of carbocyclic cyclopropyl L-nucleosides has been accomplished from L-gulonic gamma-lactone. The key intermediate 3 was stereoselectively synthesized by DIBAL-H reduction and silyl protection followed by cyclopropanation from ester 2, which was in turn prepared from L-gulonic gamma-lactone (1) in five steps. Desilylation of cyclopropyl intermediate 3 gave alcohol 4, which was then converted to the urea derivative 5 and cyclopropylamine 7 by Curtius rearrangement of an acyl azide. The urea intermediate 5 was utilized to prepare thymine 10, uracil 11, and cytosine 14 derivatives. The hypoxanthine, adenine, and guanine nucleosides 21, 22, and 24 were synthesized from the amino intermediate 7.