Project description:Electrochemical water splitting is one of the most sustainable approaches for generating hydrogen. Because of the inherent constraints associated with the architecture and materials, the conventional alkaline water electrolyzer and the emerging proton exchange membrane electrolyzer are suffering from low efficiency and high materials/operation costs, respectively. Herein, we design a membrane-free flow electrolyzer, featuring a sandwich-like architecture and a cyclic operation mode, for decoupled overall water splitting. Comprised of two physically-separated compartments with flowing H2-rich catholyte and O2-rich anolyte, the cell delivers H2 with a purity >99.1%. Its low internal ohmic resistance, highly active yet affordable bifunctional catalysts and efficient mass transport enable the water splitting at current density of 750 mA cm-2 biased at 2.1 V. The eletrolyzer works equally well both in deionized water and in regular tap water. This work demonstrates the opportunity of combining the advantages of different electrolyzer concepts for water splitting via cell architecture and materials design, opening pathways for sustainable hydrogen generation.
Project description:The increasing demand for clean energy conversion and storage has increased interest in hydrogen production via electrolytic water splitting. However, the simultaneous production of hydrogen and oxygen in this process poses a challenge in extracting pure hydrogen without using ionic conducting membranes. Researchers have developed various innovative designs to overcome this issue, but continuous water splitting in separated tanks remains a desirable approach. This study presents a novel, continuous roll-to-roll process that enables fully decoupled hydrogen evaluation reaction (HER) and oxygen evolution reaction (OER) in two separate electrolyte tanks. The system utilizes specially designed "cable-car" electrodes (CCE) that cycle between the HER and OER tanks, resulting in continuous hydrogen production with a purity of over 99.9% and Coulombic efficiency of 98% for prolonged periods. This membrane-free water splitting system offers promising prospects for scaled-up industrial-scale green hydrogen production, as it reduces the cost and complexity of the system, and allows for the use of renewable energy sources to power the electrolysis process, thus reducing the carbon footprint of hydrogen production.
Project description:Low-cost, efficient CO2-to-CO+O2 electrochemical splitting is a key step for liquid-fuel production for renewable energy storage and use of CO2 as a feedstock for chemicals. Heterogeneous catalysts for cathodic CO2-to-CO associated with an O2-evolving anodic reaction in high-energy-efficiency cells are not yet available. An iron porphyrin immobilized into a conductive Nafion/carbon powder layer is a stable cathode producing CO in pH neutral water with 90% faradaic efficiency. It is coupled with a water oxidation phosphate cobalt oxide anode in a home-made electrolyzer by means of a Nafion membrane. Current densities of approximately 1 mA/cm(2) over 30-h electrolysis are achieved at a 2.5-V cell voltage, splitting CO2 and H2O into CO and O2 with a 50% energy efficiency. Remarkably, CO2 reduction outweighs the concurrent water reduction. The setup does not prevent high-efficiency proton transport through the Nafion membrane separator: The ohmic drop loss is only 0.1 V and the pH remains stable. These results demonstrate the possibility to set up an efficient, low-voltage, electrochemical cell that converts CO2 into CO and O2 by associating a cathodic-supported molecular catalyst based on an abundant transition metal with a cheap, easy-to-prepare anodic catalyst oxidizing water into O2.
Project description:Alkaline water electrolysis is a promising low-cost strategy for clean and sustainable hydrogen production but is largely limited by the sluggish anodic oxygen evolution reaction and the challenges in maintaining adequate separation between H2 and O2. Here, we reveal an anodic-cathodic sequential oxygen evolution process via electrochemical oxidation and subsequent reduction of Ni hydroxides, enabling much lower overpotentials than conventional anodic oxygen evolution. By using (isotope-labeled) differential electrochemical mass spectrometry and in situ Raman spectroscopy combined with density functional theory calculations, we evidence that the sequential oxygen evolution originates from the electrochemical oxidation of Ni hydroxides to NiOO- active species while undergoing a different, reductive step of NiOO- for the final release of O2 due to weakened Ni-O covalency. Based on this sequential process, we propose and demonstrate a hybrid water electrolysis and energy storage device, which enables time-decoupled hydrogen and oxygen evolution and electrochemical energy storage in the Ni hydroxides.
Project description:An electrochemical approach for ammonia production is successfully developed by coupling the anodic dinitrogen oxidation reaction (NOR) and cathodic hydrogen evolution reaction (HER) within a well-designed membraneless flow electrolyzer. The obtained reactor shows the preferential yield of ammonia over nitrogen oxides on the vanadium nitride catalyst surface. At an applied oxidation potential of 2.25 V versus the reversible hydrogen electrode (vs RHE), a promoted ammonia production rate and Faradaic efficiency (FE) were obtained with 9.9 mmol g-1 h-1 (0.029 mmol cm-2 h-1) and 4.8%, respectively. Besides, the negative affection of ammonia contamination is efficiently alleviated. Density functional theory calculations revealed that the thermodynamic energy needed to produce ammonia (-0.63 eV) is far lower than that of producing nitrogen oxide (0.96 eV) from hydrogenated nitrogen oxides [∗N2OH] splitting, confirming the coupling of NOR and HER.
Project description:Green hydrogen produced by water splitting using renewable electricity is essential to achieve net-zero carbon emissions. Present water electrolysis technologies are uncompetitive with low-cost grey hydrogen produced from fossil fuels, limiting their scale-up potential. Disruptive processes that decouple the hydrogen and oxygen evolution reactions and produce them in separate cells or different stages emerge as a prospective route to reduce system cost by enabling operation without expensive membranes and sealing components. Some of these processes divide the hydrogen or oxygen evolution reactions into electrochemical and chemical sub-reactions, enabling them to achieve high efficiency. However, high efficiency has been demonstrated only in a batch process with thermal swings that present operational challenges. This work introduces a breakthrough process that produces hydrogen and oxygen in separate cells and supports continuous operation in a membraneless system. We demonstrate high faradaic and electrolytic efficiency and high rate operation in a near-neutral electrolyte of NaBr in water, whereby bromide is electro-oxidized to bromate concurrent with hydrogen evolution in one cell, and bromate is chemically reduced to bromide in a catalytic reaction that evolves oxygen in another cell. This process may lead the way to high-efficiency membraneless water electrolysis that overcomes the limitations of century-old membrane electrolysis.
Project description:As the most well-known electrocatalyst for cathodic hydrogen evolution in water splitting electrolyzers, platinum is unfortunately inefficient for anodic oxygen evolution due to its over-binding with oxygen species and excessive dissolution in oxidative environment. Herein we show that single Pt atoms dispersed in cobalt hydrogen phosphate with an unique Pt(OH)(O3)/Co(P) coordination can achieve remarkable catalytic activity and stability for oxygen evolution. The catalyst yields a high turnover frequency (35.1 ± 5.2 s-1) and mass activity (69.5 ± 10.3 A mg-1) at an overpotential of 300 mV and excellent stability. Mechanistic studies elucidate that the superior catalytic performance of isolated Pt atoms herein stems from optimal binding energies of oxygen intermediate and also their strong electronic coupling with neighboring Co atoms that suppresses the formation of soluble Ptx>4 species. Alkaline water electrolyzers assembled with an ultralow Pt loading realizes an industrial-level current density of 1 A cm-2 at 1.8 volts with a high durability.
Project description:Hydrogen production from renewable resources and its reconversion into electricity are two important pillars toward a more sustainable energy use. The efficiency and viability of these technologies heavily rely on active and stable electrocatalysts. Basic research to develop superior electrocatalysts is commonly performed in conventional electrochemical setups such as a rotating disk electrode (RDE) configuration or H-type electrochemical cells. These experiments are easy to set up; however, there is a large gap to real electrochemical conversion devices such as fuel cells or electrolyzers. To close this gap, gas diffusion electrode (GDE) setups were recently presented as a straightforward technique for testing fuel cell catalysts under more realistic conditions. Here, we demonstrate for the first time a GDE setup for measuring the oxygen evolution reaction (OER) of catalysts for proton exchange membrane water electrolyzers (PEMWEs). Using a commercially available benchmark IrO2 catalyst deposited on a carbon gas diffusion layer (GDL), it is shown that key parameters such as the OER mass activity, the activation energy, and even reasonable estimates of the exchange current density can be extracted in a realistic range of catalyst loadings for PEMWEs. It is furthermore shown that the carbon-based GDL is not only suitable for activity determination but also short-term stability testing. Alternatively, the GDL can be replaced by Ti-based porous transport layers (PTLs) typically used in commercial PEMWEs. Here a simple preparation is shown involving the hot-pressing of a Nafion membrane onto a drop-cast glycerol-based ink on a Ti-PTL.
Project description:Catalysts capable of electrochemical overall water splitting in acidic, neutral, and alkaline solution are important materials. This work develops bifunctional catalysts with single atom active sites through a pyrolysis-free route. Starting with a conjugated framework containing Fe sites, the addition of Ni atoms is used to weaken the adsorption of electrochemically generated intermediates, thus leading to more optimized energy level sand enhanced catalytic performance. The pyrolysis-free synthesis also ensured the formation of well-defined active sites within the framework structure, providing ideal platforms to understand the catalytic processes. The as-prepared catalyst exhibits efficient catalytic capability for electrochemical water splitting in both acidic and alkaline electrolytes. At a current density of 10 mA cm-2, the overpotential for hydrogen evolution and oxygen evolution is 23/201 mV and 42/194 mV in 0.5 M H2SO4 and 1 M KOH, respectively. Our work not only develops a route towards efficient catalysts applicable across a wide range of pH values, it also provides a successful showcase of a model catalyst for in-depth mechanistic insight into electrochemical water splitting.
Project description:Electrosynthesis, a viable path to decarbonize the chemical industry, has been harnessed to generate valuable chemicals under ambient conditions. Here, we present a membrane-free flow electrolyzer for paired electrocatalytic upcycling of nitrate (NO3-) and chloride (Cl-) to ammonia (NH3) and chlorine (Cl2) gases by utilizing waste streams as substitutes for traditional electrolytes. The electrolyzer concurrently couples electrosynthesis and gaseous-product separation, which minimizes the undesired redox reaction between NH3 and Cl2 and thus prevents products loss. Using a three-stacked-modules electrolyzer system, we efficiently processed a reverse osmosis retentate waste stream. This yielded high concentrations of (NH4)2SO4 (83.8 mM) and NaClO (243.4 mM) at an electrical cost of 7.1 kWh per kilogram of solid products, while residual NH3/NH4+ (0.3 mM), NO2- (0.2 mM), and Cl2/HClO/ClO- (0.1 mM) pollutants in the waste stream could meet the wastewater discharge regulations for nitrogen- and chlorine-species. This study underscores the value of pairing appropriate half-reactions, utilizing waste streams to replace traditional electrolytes, and merging product synthesis with separation to refine electrosynthesis platforms.