In Situ Synthesis of CuxO/N Doped Graphdiyne with Pyridine N Configuration for Ammonia Production via Nitrate Reduction.

Electroreduction of nitrate to ammonia provides an interesting pathway for wastewater treatment and valorization. Cu-based catalysts are active for the conversion of NO3 - to NO2 - but suffer from an inefficient hydrogenation process of NO2 -. Herein, CuxO/N-doped graphdiyne (CuxO/N-GDY) with pyridine N configuration are in situ prepared in one pot. Benefiting from the synergistic effect of pyridinic N in GDY and CuxO, the prepared CuxO/N-GDY tested in a commercial H-cell achieved a faradaic efficiency of 85% toward NH3 at -0.5 V versus RHE with a production rate of 340 µmol h-1 mgcat -1 in 0.1 M KNO3. When integrating the CuxO/N-GDY in an anion exchange membrane flow electrolyzer, a maximum Faradaic efficiency of 89% is achieved at a voltage of 2.3 V and the production rate is 1680 µmol h-1 mgcat -1 at 3.3 V in 0.1 M KNO3 at room temperature. Operation at 40 °C further promoted the overall reaction kinetics of NO3 - to NH3, but penalized its selectivity with respect to hydrogen evolution reaction. The high selectivity and production rate in this device configuration demonstrate its potential for industrial application.

Contrasting Views of the Electric Double Layer in Electrochemical CO2 Reduction: Continuum Models vs Molecular Dynamics.

In the field of electrochemical CO2 reduction, both continuum models and molecular dynamics (MD) models have been used to understand the electric double layer (EDL). MD often focuses on the region within a few nm of the electrode, while continuum models can span up to the device level (cm). Still, both methods model the EDL, and for a cohesive picture of the CO2 electrolysis system, the two methods should agree in the regions where they overlap length scales. To this end, we make a direct comparison between state-of-the-art continuum models and classical MD simulations under the conditions of CO2 reduction on a Ag electrode. For continuum modeling, this includes the Poisson-Nernst-Planck formulation with steric (finite ion size) effects, and in MD the electrode is modeled with the constant potential method. The comparison yields numerous differences between the two modeling methods. MD shows cations forming two adsorbed layers, including a fully hydrated outer layer and a partial hydration layer closer to the electrode surface. The strength of the inner adsorbed layer increases with cation size (Li+ < Na+ < K+ < Cs+) and with more negative applied potentials. Continuum models that include steric effects predict CO2 to be mostly excluded within 1 nm of the cathode due to tightly packed cations, yet we find little evidence to support these predictions from the MD results. In fact, MD shows that the concentration of CO2 increases within a few Å of the cathode surface due to interactions with the Ag electrode, a factor not included in continuum models. The EDL capacitance is computed from the MD results, showing values in the range of 7-9 µF cm-2, irrespective of the electrolyte concentration, cation identity, or applied potential. The direct comparison between the two modeling methods is meant to show the areas of agreement and disagreement between the two views of the EDL, so as to improve and better align these models.

Rate-Determining Step for Electrochemical Reduction of Carbon Dioxide into Carbon Monoxide at Silver Electrodes.

Silver is one of the most studied electrode materials for the electrochemical reduction of carbon dioxide into carbon monoxide, a product with many industrial applications. There is a growing number of reports in which silver is implemented in gas diffusion electrodes as part of a large-scale device to develop commercially relevant technology. Electrochemical models are expected to guide the design and operation toward cost-efficient devices. Despite decades of investigations, there are still uncertainties in the way this reaction should be modeled due to the absence of scientific consensus regarding the reaction mechanism and the nature of the rate-determining step. We review previously reported studies to draw converging conclusions on the value of the Tafel slope and existing species at the electrode surface. We also list conflicting experimental observations and provide leads to tackling these remaining questions.

Quantifying mass transport limitations in a microfluidic CO2 electrolyzer with a gas diffusion cathode.

A gas diffusion electrode (GDE) based CO2 electrolyzer shows enhanced CO2 transport to the catalyst surface, significantly increasing current density compared to traditional planar immersed electrodes. A two-dimensional model for the cathode side of a microfluidic CO2 to CO electrolysis device with a GDE is developed. The model, validated against experimental data, examines key operational parameters and electrode materials. It predicts an initial rise in CO partial current density (PCD), peaking at 75 mA cm-2 at -1.3 V vs RHE for a fully flooded catalyst layer, then declining due to continuous decrease in CO2 availability near the catalyst surface. Factors like electrolyte flow rate and CO2 gas mass flow rate influence PCD, with a trade-off between high CO PCD and CO2 conversion efficiency observed with increased CO2 gas flow. We observe that a significant portion of the catalyst layer remains underutilized, and suggest improvements like varying electrode porosity and anisotropic layers to enhance mass transport and CO PCD. This research offers insights into optimizing CO2 electrolysis device performance.

Probabilistic Techno-Economic Assessment of Medium-Scale Photoelectrochemical Fuel Generation Plants.

Photoelectrochemical (PEC) systems are promising approaches for sustainable fuel processing. PEC devices, like conventional photovoltaic-electrolyzer (PV-EC) systems, utilize solar energy for splitting water into hydrogen and oxygen. Contrary to PV-EC systems, PEC devices integrate the photoabsorber, the ionic membrane, and the catalysts into a single reactor. This integration of elements potentially makes PEC systems simpler in design, increases efficiency, offers a cost advantage, and allows for implementation with higher flexibility in use. We present a detailed techno-economic evaluation of PEC systems with three different device designs. We combine a system-level techno-economic analysis based on physical performance models (including degradation) with stochastic methods for uncertainty assessments, also considering the use of PV and EC learning curves for future cost scenarios. For hydrogen, we assess different PEC device design options (utilizing liquid or water vapor as reactant) and compare them to conventional PV-EC systems (anion or cation exchange). We show that in the current scenario, PEC systems (with a levelized cost of hydrogen of 6.32 $/kgH2 ) located in southern Spain are not yet competitive, operating at 64% higher costs than the PV-driven anion exchange EC systems. Our analysis indicates that PEC plants' material and size are the most significant factors affecting hydrogen costs. PEC designs operating with water vapor are the most economical designs, with the potential to cost about 10% less than PV-EC systems and to reach a 2 $/kgH2 target by 2040. If a sunlight concentrator is incorporated, the PEC-produced hydrogen cost is significantly lower (3.59 $/kgH2 in the current scenario). Versions of the concentrated PEC system that incorporate reversible operation and CO2 reduction indicate a levelized cost of storage of 0.2803 $/kWh for the former and a levelized cost of CO of 0.546 $/kgCO for the latter. These findings demonstrate the competitiveness and viability of (concentrated) PEC systems and their versatile use cases. Our study shows the potential of PEC devices and systems for hydrogen production (current and future potential), storage applications, and CO production, thereby highlighting the importance of sustainable and cost-effective design considerations for future advancements in technology development in this field.

High-throughput parallel testing of ten photoelectrochemical cells for water splitting: case study on the effects of temperature in hematite photoanodes.

High-throughput testing of photoelectrochemical cells and materials under well-defined operating conditions can accelerate the discovery of new semiconducting materials, the characterization of the phenomena occurring at the semiconductor-electrolyte interface, or the understanding of the coupled multi-physics transport phenomena of a complete working cell. However, there have been few high-throughput systems capable of dealing with complete cells and applying variations in real-life operating conditions, like temperature or irradiance. Understanding the effects of the variations of these real-life operating conditions on the performance of photoelectrode materials requires reliable and reproducible measurements. In this work, we report on a setup that simultaneously tests ten individual, identical photoelectrochemical cells whilst controlling temperature. The effects of temperature from 26 to 65 °C were studied in tin-doped hematite photoanodes for water splitting - as a reference case - through cyclic voltammetry and electrochemical impedance spectroscopy. The increase of surface-state-mediated charge recombination with temperature mainly penalized the energy conversion efficiency due to the reduction of the photovoltage produced. For parallel measurements in the ten individual cells, standard deviations from 20 to 60 mV for the onset potentials and less than 0.2 mA cm-2 for saturation current densities quantified the reproducibility of the results.

Stability and degradation of (oxy)nitride photocatalysts for solar water splitting.

Advancing towards alternative technologies for the sustainable production of hydrogen is a necessity for the successful integration of this potentially green fuel in the future. Photocatalytic and photoelectrochemical water splitting are promising concepts in this context. Over the past decades, researchers have successfully explored several materials classes, such as oxides, nitrides, and oxynitrides, in their quest for suitable photocatalysts with a focus on reaching higher efficiencies. However, to pave the way towards practicability, understanding degradation processes and reaching stability is essential, a domain where research has been scarcer. This perspective aims at providing an overview on recent progress concerning stability and degradation with a focus on (oxy)nitride photocatalysts and at providing insights into the opportunities and challenges coming along with the investigation of degradation processes and the attempts to improve the stability of photocatalysts.

ICP-MS Assisted EDX Tomography: A Robust Method for Studying Electrolyte Penetration Phenomena in Gas Diffusion Electrodes Applied to CO2 Electrolysis.

A carbon paper-based gas diffusion electrode (GDE) is used with a bismuth(III) subcarbonate active catalyst phase for the electrochemical reduction of CO2 in a gas/electrolyte flow-by configuration electrolyser at high current density. It is demonstrated that in this configuration, the gas and catholyte phases recombine to form K2CO3/KHCO3 precipitates to an extent that after electrolyses, vast amount of K+ ions is found by EDX mapping in the entire GDE structure. The fact that the entirety of the GDE gets wetted during electrolysis should, however, not be interpreted as a sign of flooding of the catalyst layer, since electrolyte perspiring through the GDE can largely be removed with the outflow gas, and the efficiency of electrolysis (toward the selective production of formate) can thus be maintained high for several hours. For a full spatial scale quantitative monitoring of electrolyte penetration into the GDE, (relying on K+ ions as tracer) the method of inductively coupled plasma-mass spectrometry (ICP-MS) assisted energy dispersive X-ray (EDX) tomography is introduced. This new, cheap and robust tomography of non-uniform aspect ratio has a large planar span that comprises the entire GDE surface area and a submicrometer depth resolution, hence it can provide quantitative information about the amount and distribution of K+ remnants inside the GDE structure, in three dimensions.