Synergistic Electrochemical CO₂ Reduction and Water Oxidation with a Bipolar Membrane

The electrochemical conversion of CO₂ and water to value-added products still suffers from low efficiency, high costs, and high sensitivity to electrolyte, pH, and contaminants. Here, we present a strategy for this reaction using a silver catalyst for CO₂ reduction in a neutral catholyte, separated by a bipolar membrane from a nickel iron hydroxide oxygen evolution catalyst in a basic anolyte. This combination of electrolytes provides a favorable environment for both catalysts and shows the effective use of bicarbonate and KOH to obtain low cell voltages. This architecture brings down the total cell voltage by more than 1 V compared to that with conventional use of a Pt counter electrode and monopolar membranes, and at the same time, it reduces contamination and improves stability at the cathode

General Considerations for Improving Photovoltage in Metal–Insulator–Semiconductor Photoanodes

Metal–insulator–semiconductor (MIS) photoelectrodes offer a simple alternative to the traditional semiconductor–liquid junction and the conventional p–n junction electrode. Highly efficient MIS photoanodes require interfacial surface passivating oxides and high workfunction metals to produce a high photovoltage. Herein, we investigate and analyze the effect of interfacial oxides and metal workfunctions on the barrier height and the photovoltage of a c-Si photoanode. We use two metal components in a bimetal contact configuration and observe the modulation of the effective barrier height and the resulting photovoltage as a function of the secondary outer metal. The photovoltage shows a strong linear dependence by increasing the inner metal workfunction, with the highest photovoltage achieved by a MIS photoanode using a platinum inner metal. We also found that coupling a thin aluminium oxide with an interfacial silicon oxide and controlling the oxide thickness can significantly improve the photovoltage of an MIS junction photoanode

In Situ Observation of Active Oxygen Species in Fe-Containing Ni-Based Oxygen Evolution Catalysts: The Effect of pH on Electrochemical Activity

Ni-based oxygen evolution catalysts (OECs) are cost-effective and very active materials that can be potentially used for efficient solar-to-fuel conversion process toward sustainable energy generation. We present a systematic spectroelectrochemical characterization of two Fe-containing Ni-based OECs, namely nickel borate (Ni­(Fe)−B_i) and nickel oxyhydroxide (Ni­(Fe)­OOH). Our Raman and X-ray absorption spectroscopy results show that both OECs are chemically similar, and that the borate anions do not play an apparent role in the catalytic process at pH 13. Furthermore, we show spectroscopic evidence for the generation of negatively charged sites in both OECs (NiOO^–), which can be described as adsorbed “active oxygen”. Our data conclusively links the OER activity of the Ni-based OECs with the generation of those sites on the surface of the OECs. The OER activity of both OECs is strongly pH dependent, which can be attributed to a deprotonation process of the Ni-based OECs, leading to the formation of the negatively charged surface sites that act as OER precursors. This work emphasizes the relevance of the electrolyte effect to obtain catalytically active phases in Ni-based OECs, in addition to the key role of the Fe impurities. This effect should be carefully considered in the development of Ni-based compounds meant to catalyze the OER at moderate pHs. Complementarily, UV–vis spectroscopy measurements show strong darkening of those catalysts in the catalytically active state. This coloration effect is directly related to the oxidation of nickel and can be an important factor limiting the efficiency of solar-driven devices utilizing Ni-based OECs

Hot Carrier Generation and Extraction of Plasmonic Alloy Nanoparticles

The conversion of light to electrical and chemical energy has the potential to provide meaningful advances to many aspects of daily life, including the production of energy, water purification, and optical sensing. Recently, plasmonic nanoparticles (PNPs) have been increasingly used in artificial photosynthesis (e.g., water splitting) devices in order to extend the visible light utilization of semiconductors to light energies below their band gap. These nanoparticles absorb light and produce hot electrons and holes that can drive artificial photosynthesis reactions. For n-type semiconductor photoanodes decorated with PNPs, hot charge carriers are separated by a process called hot electron injection (HEI), where hot electrons with sufficient energy are transferred to the conduction band of the semiconductor. An important parameter that affects the HEI efficiency is the nanoparticle composition, since the hot electron energy is sensitive to the electronic band structure of the metal. Alloy PNPs are of particular importance for semiconductor/PNPs composites, because by changing the alloy composition their absorption spectra can be tuned to accurately extend the light absorption of the semiconductor. This work experimentally compares the HEI efficiency from Ag, Au, and Ag/Au alloy nanoparticles to TiO₂ photoanodes for the photoproduction of hydrogen. Alloy PNPs not only exhibit tunable absorption but can also improve the stability and electronic and catalytic properties of the pure metal PNPs. In this work, we find that the Ag/Au alloy PNPs extend the stability of Ag in water to larger applied potentials while, at the same time, increasing the interband threshold energy of Au. This increasing of the interband energy of Au suppresses the visible-light-induced interband excitations, favoring intraband excitations that result in higher hot electron energies and HEI efficiencies

Solar Water Splitting Combining a BiVO₄ Light Absorber with a Ru-Based Molecular Cocatalyst

We demonstrate here for the first time the photoelectrochemical properties of a BiVO₄ photoanode in conjunction with a <i>molecular</i> catalyst. When the Ru-based molecular catalyst (RuCat) is coupled to a BiVO₄ light-absorber the performance of this photoanode improves particularly in the low-bias region (<1.0 V vs RHE). The RuCat-BiVO₄ photoanode shows a higher photocurrent than CoP_i-BiVO₄ under front illumination, and a 0.1 V more cathodic onset potential. The former can be partly explained by the low light absorption of the RuCat (<5% light absorption in the UV–vis–NIR range). For the latter, we propose that the linkers in the RuCat reduce the surface recombination in BiVO₄ to a greater extent than CoP_i. Finally, we observe that the fill factor of the RuCat-BiVO₄ JV characteristic improves after the stability test. The results presented herein not only show the feasibility and potential of the solid state/molecular heterojunctions but also represent a proof of principle to improve conventional all-solid-state systems such as CoP_i-BiVO₄

Elucidation of Critical Catalyst Layer Phenomena toward High Production Rates for the Electrochemical Conversion of CO to Ethylene

This work utilizes EIS to elucidate the impact of catalyst–ionomer interactions and cathode hydroxide ion transport resistance (RCL,OH–) on cell voltage and product selectivity for the electrochemical conversion of CO to ethylene. When using the same Cu catalyst and a Nafion ionomer, varying ink dispersion and electrode deposition methods results in a change of 2 orders of magnitude for RCL,OH– and ca. a 25% change in electrode porosity. Decreasing RCL,OH– results in improved ethylene Faradaic efficiency (FE), up to ∼57%, decrease in hydrogen FE, by ∼36%, and reduction in cell voltage by up to 1 V at 700 mA/cm2. Through the optimization of electrode fabrication conditions, we achieve a maximum of 48% ethylene with >90% FE for non-hydrogen products in a 25 cm2 membrane electrode assembly at 700 mA/cm2 and RCL,OH– is translated to other material requirements, such as anode porosity. We find that the best performing electrodes use ink dispersion and deposition techniques that project well into roll-to-roll processes, demonstrating the scalability of the optimized process