Understanding Multi-Ion Transport Mechanisms in Bipolar Membranes.

Bipolar membranes (BPMs) have the potential to become critical components in electrochemical devices for a variety of electrolysis and electrosynthesis applications. Because they can operate under large pH gradients, BPMs enable favorable environments for electrocatalysis at the individual electrodes. Critical to the implementation of BPMs in these devices is understanding the kinetics of water dissociation that occurs within the BPM as well as the co- and counter-ion crossover through the BPM, which both present significant obstacles to developing efficient and stable BPM-electrolyzers. In this study, a continuum model of multi-ion transport in a BPM is developed and fit to experimental data. Specifically, concentration profiles are determined for all ionic species, and the importance of a water-dissociation catalyst is demonstrated. The model describes internal concentration polarization and co- and counter-ion crossover in BPMs, determining the mode of transport for ions within the BPM and revealing the significance of salt-ion crossover when operated with pH gradients relevant to electrolysis and electrosynthesis. Finally, a sensitivity analysis reveals that the performance and lifetime of BPMs can be improved substantially by using of thinner dissociation catalysts, managing water transport, modulating the thickness of the individual layers in the BPM to control salt-ion crossover, and increasing the ion-exchange capacity of the ion-exchange layers in order to amplify the water-dissociation kinetics at the interface.

A direct coupled electrochemical system for capture and conversion of CO2 from oceanwater.

Capture and conversion of CO2 from oceanwater can lead to net-negative emissions and can provide carbon source for synthetic fuels and chemical feedstocks at the gigaton per year scale. Here, we report a direct coupled, proof-of-concept electrochemical system that uses a bipolar membrane electrodialysis (BPMED) cell and a vapor-fed CO2 reduction (CO2R) cell to capture and convert CO2 from oceanwater. The BPMED cell replaces the commonly used water-splitting reaction with one-electron, reversible redox couples at the electrodes and demonstrates the ability to capture CO2 at an electrochemical energy consumption of 155.4 kJ mol-1 or 0.98 kWh kg-1 of CO2 and a CO2 capture efficiency of 71%. The direct coupled, vapor-fed CO2R cell yields a total Faradaic efficiency of up to 95% for electrochemical CO2 reduction to CO. The proof-of-concept system provides a unique technological pathway for CO2 capture and conversion from oceanwater with only electrochemical processes.

Improving the Back Surface Field on an Amorphous Silicon Carbide Thin-Film Photocathode for Solar Water Splitting.

Amorphous silicon carbide (a-SiC:H) is a promising material for photoelectrochemical water splitting owing to its relatively small band-gap energy and high chemical and optoelectrical stability. This work studies the interplay between charge-carrier separation and collection, and their injection into the electrolyte, when modifying the semiconductor/electrolyte interface. By introducing an n-doped nanocrystaline silicon oxide layer into a p-doped/intrinsic a-SiC:H photocathode, the photovoltage and photocurrent of the device can be significantly improved, reaching values higher than 0.8 V. This results from enhancing the internal electric field of the photocathode, reducing the Shockley-Read-Hall recombination at the crucial interfaces because of better charge-carrier separation. In addition, the charge-carrier injection into the electrolyte is enhanced by introducing a TiO2 protective layer owing to better band alignment at the interface. Finally, the photocurrent was further enhanced by tuning the absorber layer thickness, arriving at a thickness of 150 nm, after which the current saturates to 10 mA cm-2 at 0 V vs. the reversible hydrogen electrode in a 0.2 m aqueous potassium hydrogen phthalate (KPH) electrolyte at pH 4.

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.

Interfacial engineering of metal-insulator-semiconductor junctions for efficient and stable photoelectrochemical water oxidation.

Solar-assisted water splitting can potentially provide an efficient route for large-scale renewable energy conversion and storage. It is essential for such a system to provide a sufficiently high photocurrent and photovoltage to drive the water oxidation reaction. Here we demonstrate a photoanode that is capable of achieving a high photovoltage by engineering the interfacial energetics of metal-insulator-semiconductor junctions. We evaluate the importance of using two metals to decouple the functionalities for a Schottky contact and a highly efficient catalyst. We also illustrate the improvement of the photovoltage upon incidental oxidation of the metallic surface layer in KOH solution. Additionally, we analyse the role of the thin insulating layer to the pinning and depinning of Fermi level that is responsible to the resulting photovoltage. Finally, we report the advantage of using dual metal overlayers as a simple protection route for highly efficient metal-insulator-semiconductor photoanodes by showing over 200 h of operational stability.