High temperature electrocatalysts based on double perovskite cobaltites that are typically employed in proton ceramic fuel cells and electrolyzers are exploited here for room temperature water oxidation. The double perovskites are assessed by the RctCdl product and we show that their intrinsic catalytic activities exceed that of IrO2.
Water electrolysis provides efficient and cost-effective production of hydrogen from renewable energy. Currently, the oxidation half-cell reaction relies on noble-metal catalysts, impeding widespread application. In order to adopt water electrolyzers as the main hydrogen production systems, it is critical to develop inexpensive and earth-abundant catalysts. This review discusses the proton exchange membrane (PEM) water electrolysis (WE) and the progress in replacing the noble-metal catalysts with earth-abundant ones. Researchers within this field are aiming to improve the efficiency and stability of earth-abundant catalysts (EACs), as well as to discover new ones. The latter is particularly important for the oxygen evolution reaction (OER) under acidic media, where the only stable and efficient catalysts are noble-metal oxides, such as IrOx and RuOx. On the other hand, there is significant progress on EACs for the hydrogen evolution reaction (HER) in acidic conditions, but how many of these EACs have been used in PEM WEs and tested under realistic conditions? What is the current status on the development of EACs for the OER? These are the two main questions this review addresses.
In order to adopt water electrolyzers as a main hydrogen production system, it is critical to develop inexpensive and earth-abundant catalysts. Currently, both half-reactions in water splitting depend heavily on noble metal catalysts. This review discusses the proton exchange membrane (PEM) water electrolysis (WE) and the progress in replacing the noble-metal catalysts with earth-abundant ones. The efforts within this field for the discovery of efficient and stable earth-abundant catalysts (EACs) have increased exponentially the last few years. The development of EACs for the oxygen evolution reaction (OER) in acidic media is particularly important, as the only stable and efficient catalysts until now are noble-metal oxides, such as IrOx and RuOx. On the hydrogen evolution reaction (HER) side, there is significant progress on EACs under acidic conditions, but there are very few reports of these EACs employed in full PEM WE cells. These two main issues are reviewed, and we conclude with prospects for innovation in EACs for the OER in acidic environments, as well as with a critical assessment of the few full PEM WE cells assembled with EACs.
Water electrolysis provides efficient and cost-effective production of hydrogen from renewable energy. Currently, the oxidation half-cell reaction relies on noble-metal catalysts, impeding widespread application. In order to adopt water electrolyzers as the main hydrogen production systems, it is critical to develop inexpensive and earth-abundant catalysts. This review discusses the proton exchange membrane (PEM) water electrolysis (WE) and the progress in replacing the noble-metal catalysts with earth-abundant ones. Researchers within this field are aiming to improve the efficiency and stability of earth-abundant catalysts (EACs), as well as to discover new ones. The latter is particularly important for the oxygen evolution reaction (OER) under acidic media, where the only stable and efficient catalysts are noble-metal oxides, such as IrOx and RuOx. On the other hand, there is significant progress on EACs for the hydrogen evolution reaction (HER) in acidic conditions, but how many of these EACs have been used in PEM WEs and tested under realistic conditions? What is the current status on the development of EACs for the OER? These are the two main questions this review addresses.
The improvement of indoor environments is of great importance as it can significantly improve human health, comfort and productivity. Herein, different forms of TiO2 nanorods were used as the photocatalyst for generation of reactive oxygen species (ROS) in a gas phase photoreactor under controlled humidity. Several parameters were investigated by monitoring the remote decolourisation of Methylene Blue (MB) embedded in a Nafion film. A decolourisation of 26% under 80% relative humidity was observed when the MB film was 0.5 cm away from the photocatalyst. The length and ratio of light/dark intervals have major impacts on the efficiency of the gas phase photocatalytic process, which we link to the amount of water adsorbed on the photocatalyst, as the source for hydroxyl radicals. Furthermore, the photocatalytic production of ROS was quantified through a polyaniline electrochemical sensor and a rate of 1 · 1012 of ROS molecules s−1 was estimated. This study contributes to the efficacy of the gas phase photocatalytic method in air decontamination, for the development of efficient air cleaning devices.
We have fabricated and tested a photoelectrochemical (PEC) cell where the aqueous electrolyte has been replaced by a proton conducting hydrated Nafion® polymer membrane. The membrane was sandwiched between a TiO2-based photoanode and a Pt/C-based cathode. The performance was tested with two types of photoanode electrodes, a thermally prepared TiO2 film on Ti foil (T-TiO2) and a nanostructured TiO2 films in the form of highly ordered nanotubes (TNT) of different lengths. Firstly, photovoltammetry experiments were conducted under asymmetric conditions, where the anode was immersed in deionized water, while the cathode was kept in ambient air. The results showed a high incident photon-to-current efficiency (IPCE) of 19% under unassisted conditions (short-circuit, 0 V vs. cathode) with short TNT (ca. 1 μm) under 4 mW cm−2 illumination with UV-A rich light. Secondly, the deionized water was replaced by 0.5 M Na2SO4 and now the performance was higher with longer nanotubes, assigned to increased ionic conductivity inside the tubes. An unassisted (0 V) IPCE of 33% was achieved with nanotubes of ca. 8 μm. The presented solid-state PEC cell minimizes the electrode distance and volume of the device, and provides a way towards compact practical applications in solar water splitting.
Mimicking natural photosynthesis by direct photoelectrochemical (PEC) reduction of CO2 to chemicals and fuels requires complex cell assemblies with limitations in selectivity, efficiency, cost, and stability. Here, we present a breakthrough cathode utilizing an oxygen tolerant formate dehydrogenase enzyme derived from clostridium carboxidivorans and coupled to a novel and efficient in situ nicotinamide adenine dinucleotide (NAD+/NADH) regeneration mechanism through interfacial electrochemistry on g-C3N4 films. We demonstrate stable (20 h) aerobic PEC CO2-to-formate reduction at close to 100 % faradaic efficiency and unit selectivity in a bio-hybrid PEC cell of minimal engineering with optimized Ta3N5 nanotube photoanode powered by simulated sunlight with a solar to fuel efficiency of 0.063 %, approaching that of natural photosynthesis.
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