Solar Hydrogen Generation from Ambient Humidity Using Functionalized Porous Photoanodes

Solar hydrogen is a promising sustainable energy vector, and steady progress has been made in the development of photoelectrochemical (PEC) cells. Most research in this field has focused on using acidic or alkaline liquid electrolytes for ionic transfer. However, the performance is limited by (i) scattering of light and blocking of catalytic sites by gas bubbles and (ii) mass transport limitations. An attractive alternative to a liquid water feedstock is to use the water vapor present as humidity in ambient air, which has been demonstrated to mitigate the above problems and can expand the geographical range where these devices can be utilized. Here, we show how the functionalization of porous TiO2 and WO3 photoanodes with solid electrolytes—proton conducting Aquivion and Nafion ionomers—enables the capture of water from ambient air and allows subsequent PEC hydrogen production. The optimization strategy of photoanode functionalization was examined through testing the effect of ionomer loading and the ionomer composition. Optimized functionalized photoanodes operating at 60% relative humidity (RH) and Tcell = 30–70 °C were able to recover up to 90% of the performance obtained at 1.23 V versus reverse hydrogen electrode (RHE) when water is introduced in the liquid phase (i.e., conventional PEC operation). Full performance recovery is achieved at a higher applied potential. In addition, long-term experiments have shown remarkable stability at 60% RH for 64 h of cycling (8 h continuous illumination–8 h dark), demonstrating that the concept can be applicable outdoors.</p

Enhanced Catalytic Probe Design for Mapping Radical Density in the Plasma Afterglow

The electrification of chemical processes using plasma generates an increasing demand for sensors, monitoring concentrations of plasma-activated species such as radicals. Radical probes are a low-cost in situ method for spatially resolved quantification of the radical density in a plasma afterglow using the heat from the exothermal recombination of radicals on a catalytic surface. However, distinguishing recombination heating from other heat fluxes in the system is challenging. In this study, we present a heat flux analysis based on probe measurements inside the reactor, with simultaneous IR imaging monitoring of the temperature of the reactor wall. The impact of radiation heat on a single thermocouple as well as the advantage of a dual thermocouple setup (using a catalytic unit together with a reference thermocouple) is shown. We add a heat sink with a monitored temperature to the dual thermocouple setup, allowing the determination of conductive and radiative heat fluxes. The heat sink gives more information on the measurement and reduces ambiguities in the evaluation used by others. The probe was tested by mapping N atom densities throughout the plasma afterglow of our reactor, enabling evaluation of the recombination kinetics of the radicals in the gas phase. Three-body recombination was shown to be the main pathway of recombination, with a recombination rate of krec = (2.0 ± 0.9)·10-44 m6/s, which is in line with the known literature findings, demonstrating that the measured species are N radicals and the probe did not influence the plasma or recombination reactions in the afterglow.</p

Plasma activated electrolysis for cogeneration of nitric oxide and hydrogen from water and nitrogen

With increasing global interest in renewable energy technology given the backdrop of climate change, storage of electrical energy has become particularly relevant. Most sustainable technologies (e.g., wind and solar) produce electricity intermittently. Thus, converting electrical energy and base molecules (i.e., H2O, N2) into energy-rich ones (e.g., H2, NH3) or chemical feedstock (e.g., NO) is of paramount importance. While H2O splitting is compatible with renewable electricity, N2 fixation is currently dominated by thermally activated processes. In this work, we demonstrate an all-electric route for simultaneous NO and H2 production. In our approach, H2O is reduced to H2 in the cathode of a solid oxide electrolyzer while NO is produced in the anode by the reaction of O2– species (transported via the electrolyte) and plasma-activated N2 species. High faradaic efficiencies up to 93% are achieved for NO production at 650 °C, and NO concentration is &gt;1000 times greater than the equilibrium concentration at the same temperature and pressure.</p

Enhancing the Electrocatalytic Activity of Redox Stable Perovskite Fuel Electrodes in Solid Oxide Cells by Atomic Layer-Deposited Pt Nanoparticles

The carbon dioxide and steam co-electrolysis in solid oxide cells offers an efficient way to store the intermittent renewable electricity in the form of syngas (CO + H2), which constitutes a key intermediate for the chemical industry. The co-electrolysis process, however, is challenging in terms of materials selection. The cell composites, and particularly the fuel electrode, are required to exhibit adequate stability in redox environments and coking that rules out the conventional Ni cermets. La0.75Sr0.25Cr0.5Mn0.5O3 (LSCrM) perovskite oxides represent a promising alternative solution, but with electrocatalytic activity inferior to the conventional Ni-based cermets. Here, we report on how the electrochemical properties of a state-of-the-art LSCrM electrode can be significantly enhanced by introducing uniformly distributed Pt nanoparticles (18 nm) on its surface via the atomic layer deposition (ALD). At 850 °C, Pt nanoparticle deposition resulted in a ∼62% increase of the syngas production rate during electrolysis mode (at 1.5 V), whereas the power output was improved by ∼84% at fuel cell mode. Our results exemplify how the powerful ALD approach can be employed to uniformly disperse small amounts (∼50 μg·cm–2) of highly active metals to boost the limited electrocatalytic properties of redox stable perovskite fuel electrodes with efficient material utilization.</p

Symmetrical Exsolution of Rh Nanoparticles in Solid Oxide Cells for Efficient Syngas Production from Greenhouse Gases

Carbon dioxide and steam solid oxide co-electrolysis is a key technology for exploiting renewable electricity to generate syngas feedstock for the Fischer–Tropsch synthesis. The integration of this process with methane partial oxidation in a single cell can eliminate or even reverse the electrical power demands of co-electrolysis, while simultaneously producing syngas at industrially attractive H2/CO ratios. Nevertheless, this system is rather complex and requires catalytically active and coke tolerant electrodes. Here, we report on a low-substitution rhodium-titanate perovskite (La0.43Ca0.37Rh0.06Ti0.94O3) electrode for the process, capable of exsolving high Rh nanoparticle populations, and assembled in a symmetrical solid oxide cell configuration. By introducing dry methane to the anode compartment, the electricity demands are impressively decreased, even allowing syngas and electricity cogeneration. To provide further insight on the Rh nanoparticles role on methane-to-syngas conversion, we adjusted their size and population by altering the reduction temperature of the perovskite. Our results exemplify how the exsolution concept can be employed to efficiently exploit noble metals for activating low-reactivity greenhouse gases in challenging energy-related applications.</p

FeP Nanocatalyst with Preferential [010] Orientation Boosts the Hydrogen Evolution Reaction in Polymer-Electrolyte Membrane Electrolyzer

The development of nonprecious metal electrocatalysts for polymer-electrolyte membrane (PEM) water electrolysis is a milestone for the technology, which currently relies on rare and expensive platinum-group metals. Half-cell measurements have shown iron phosphide materials to be promising alternative hydrogen evolution electrocatalysts, but their realistic performance in flow-through devices remains unexplored. To fill this gap, we report herein the activity and durability of FeP nanocatalyst under application-relevant conditions. Our facile synthesis route proceeds via impregnation of an iron complex on conductive carbon support followed by phosphorization, giving rise to highly crystalline nanoparticles with predominantly exposed [010] facets, which accounts for the high electrocatalytic activity. The performance of FeP gas diffusion electrodes toward hydrogen evolution was examined under application-relevant conditions in a single cell PEM water electrolysis at 22 °C. The FeP cathode exhibited a current density of 0.2 A cm–2 at 2.06 V, corresponding to a difference of merely 0.07 W cm–2 in power input as compared to state-of-the-art Pt cathode, while outperforming other nonprecious cathodes operated at similar temperature. Quantitative product analysis of our PEM device excluded the presence of side reactions and provided strong experimental evidence that our cell operates with 84–100% Faradaic efficiencies and with 4.1 kWh Nm–3 energy consumption. The FeP cathodes exhibited stable performance of over 100 h at constant operation, while their suitability with the intermittency of renewable sources was demonstrated upon 36 h operation at variable power inputs. Overall, the performance as well as our preliminary cost analysis reveal the high potential of FeP for practical applications.</p

An Efficient Strategy for Electroreduction Reactor Outlet Fractioning into Valuable Products

In this work, two industrial dual-step pressure swing adsorption (PSA) processes were designed and simulated to obtain high-purity methane, CO2, and syngas from a gas effluent of a CO2 electroreduction reactor using different design configurations. Among the set of zeolites that was investigated using Monte Carlo and molecular dynamics simulations, NaX and MFI were the ones selected. The dual-PSA process for case study 1 is only capable of achieving a 90.5% methane purity with a 95.2% recovery. As for case study 2, methane is obtained with a 97.5% purity and 95.3% recovery. Both case studies can produce CO2 with high purity and recovery (&gt;97 and 95%, respectively) and syngas with a H2/CO ratio above 4. Although case study 2 allows methane to be used as domestic gas, a much higher value for its energy consumption is observed compared to case study 1 (64.9 vs 29.8 W h molCH4-1).</p

Hydrogen from electrochemical reforming of C1–C3 alcohols using proton conducting membranes

This study investigates the production of hydrogen from the electrochemical reforming of short-chain alcohols (methanol, ethanol, iso-propanol) and their mixtures. High surface gas diffusion Pt/C electrodes were interfaced to a Nafion polymeric membrane. The assembly separated the two chambers of an electrochemical reactor, which were filled with anolyte (alcohol&nbsp;+&nbsp;H2O or alcohol&nbsp;+&nbsp;H2SO4) and catholyte (H2SO4) aqueous solutions. The half-reactions, which take place upon polarization, are the alcohol electrooxidation and the hydrogen evolution reaction at the anode and cathode, respectively. A standard Ag/AgCl reference electrode was introduced for monitoring the individual anodic and cathodic overpotentials. Our results show that roughly 75% of the total potential losses are due to sluggish kinetics of the alcohol electrooxidation reaction. Anodic overpotential becomes larger as the number of C-atoms in the alcohol increases, while a slight dependence on the pH was observed upon changing the acidity of the anolyte solution. In the case of alcohol mixtures, it is the largest alcohol that dictates the overall cell performance. © 2017 Hydrogen Energy Publications LLC</p

An Electrochemical Study on the Cathode of the Intermediate Temperature Tubular Sodium-Sulfur (NaS) Battery

The development of low-cost energy storage schemes is imminent in light of the ever-growing demand of electricity. Sodium-sulfur (NaS) batteries offer low-cost technology for energy storage applications due to the intrinsically high capacities of elemental sodium and sulfur as well as their abundant resources. Operating this battery technology on the intermediate range (130-200 degrees C) can lead to lower material costs, mitigate thermal management and safety issues and enhance cycle life. Herein, an electrochemical study on the cathode of the IT NaS cell is performed at 150 degrees C and a concentration range of 1.5 to 3 M sodium pentasulfide dissolved in tetraglyme, showing a robust long term performance (42 days of continuous cycling) with a volumetric energy density of 83 Wh L-1. Most importantly, the cell was eligible for a tenfold volume scale-up considerably enhancing its capacity (790 mAh) but in the same time somewhat hindered by mass transport, especially during the end of the discharge process as manifested by electrochemical impedance spectroscopy.</p