Efficient Water Oxidation Research Articles

Dual Cocatalysts Synergistically Promote Perylene Diimide Polymer Charge Transfer for Enhanced Photocatalytic Water Oxidation

Water oxidation is a critical reaction in artificial photosynthesis which is limited by a high reaction energy barrier and often requires matching cocatalysts. Dual cocatalysts Co3O4 and Pt are combined with a perylene diimide (PDI) polymer, accomplishing a photocatalytic O2 production rate of 24.4 mmol g–1 h–1 under visible light irradiation, which is a 5.4-fold enhancement compared with PDI alone. Moreover, the apparent quantum yield of the O2 evolution reaction reaches 6.9% at 420 nm and remains 1.2% at 590 nm. The dual cocatalysts-constructed interfacial electric fields provide an anisotropic driving force for photogenerated holes to Co3O4 and electrons to Pt, synergistically improving the spatial charge separation efficiency for water oxidation. Co3O4 molecules serve as active sites for the water oxidation reaction to improve the utilization of photogenerated holes on the surface. This work provides a valuable demonstration of the interaction process and mechanism of cocatalysts, guiding the selection of cocatalysts for high-efficiency solar energy conversion.

Fe(III) Docking-Activated Sites in Layered Birnessite for Efficient Water Oxidation

Non-noble metal catalysts for promoting the sluggish kinetics of oxygen evolution reaction (OER) are essential to efficient water splitting for sustainable hydrogen production. Birnessite has a local atomic structure similar to that of an oxygen-evolving complex in photosystem II, while the catalytic activity of birnessite is far from satisfactory. Herein, we report a novel Fe-Birnessite (Fe-Bir) catalyst obtained by controlled Fe(III) intercalation- and docking-induced layer reconstruction. The reconstruction dramatically lowers the OER overpotential to 240 mV at 10 mA/cm2 and the Tafel slope to 33 mV/dec, making Fe-Bir the best of all the reported Bir-based catalysts, even on par with the best transition-metal-based OER catalysts. Experimental characterizations and molecular dynamics simulations elucidate that the catalyst features active Fe(III)-O-Mn(III) centers interfaced with ordered water molecules between neighboring layers, which lower reorganization energy and accelerate electron transfer. DFT calculations and kinetic measurements show non-concerted PCET steps conforming to a new OER mechanism, wherein the neighboring Fe(III) and Mn(III) synergistically co-adsorb OH* and O* intermediates with a substantially reduced O-O coupling activation energy. This work highlights the importance of elaborately engineering the confined interlayer environment of birnessite and more generally, layered materials, for efficient energy conversion catalysis.

Silver nanoparticles embedded in phosphorus and nitrogen-doped hierarchical hollow porous carbon for efficient supercapacitor and electrocatalytic water oxidation

Supercapacitor (SC) and oxygen evolution reaction (OER) require highly efficient multifunctional catalysts prepared from non-noble metals and heteroatoms. In this work, we have developed silver (Ag) decorated on phosphorus (P), nitrogen (N) -doped hollow porous carbon (HPC) prepared through hydrothermal followed by pyrolysis method. The prepared bifunctional electrocatalyst was studied through different characterization techniques. As-prepared HPC-UD, P-HPC-UD, and Ag@P-HPC-UD integrate high-level P-doping, large specific surface areas (up to 1452, 1247, and 528 m2 g−1), and hierarchical multipores of cross-linked micro and mesopore channels. As a result, the Ag and P modified the active sites and electronic structure of the HPC bifunctional catalyst, which is beneficial for the electrocatalytic process. As a result, the Ag@P-HPC-UD catalyst provides an outstanding specific capacitance value of 388 F g−1 at 0.5 A g−1 when used as a SC electrode. Furthermore, the Ag@P-HPC-UD electrocatalyst exhibited efficient OER behavior with a lower overpotential of 165 mV at 10 mA cm−2 current density and a lower Tafel value of 55.46 mV dec−1, which is remarkably superior to commercial RuO2 electrocatalyst. Therefore, the Ag@P-HPC-UD electrocatalyst pathway for a new revolution in developing a highly impressive carbon-based electrode towards both SC and electrocatalytic OER performance.

Construction of Zn-doped RuO2 nanowires for efficient and stable water oxidation in acidic media

Oxygen evolution reaction catalysts capable of working efficiently in acidic media are highly demanded for the commercialization of proton exchange membrane water electrolysis. Herein, we report a Zn-doped RuO2 nanowire array electrocatalyst with outstanding catalytic performance for the oxygen evolution reaction under acidic conditions. Overpotentials as low as 173, 304, and 373 mV are achieved at 10, 500, and 1000 mA cm−2, respectively, with robust stability reaching to 1000 h at 10 mA cm−2. Experimental and theoretical investigations establish a clear synergistic effect of Zn dopants and oxygen vacancies on regulating the binding configurations of oxygenated adsorbates on the active centers, which then enables an alternative Ru−Zn dual-site oxide path of the reaction. Due to the change of reaction pathways, the energy barrier of rate-determining step is reduced, and the over-oxidation of Ru active sites is alleviated. As a result, the catalytic activity and stability are significantly enhanced.

Enriched Fe Doped on Amorphous Shell Enable Crystalline@Amorphous Core-Shell Nanorod Highly Efficient Electrochemical Water Oxidation.

The rational design of efficient and cost-effective electrocatalysts for oxygen evolution reaction (OER) with sluggish kinetics, is imperative to diverse clean energy technologies. The performance of electrocatalyst is usually governed by the number of active sites on the surface. Crystalline/amorphous heterostructure has exhibited unique properties and opens new paradigms toward designing electrocatalysts with abundant active sites for improved performance. Hence, Fe doped Ni-Co phosphite (Fe-NiCoHPi) electrocatalyst with cauliflower-like structure, comprising crystalline@amorphous core-shell nanorod, is reported. The experiments uncover that Fe is enriched in the amorphous shell due to the flexibility of the amorphous component. Further density functional theory calculations indicate that the strong electronic interaction between the enriched Fe in the amorphous shell and crystalline core host at the core-shell interface, leads to balanced binding energies of OER intermediates, which is the origin of the catalyst-activity. Eventually, the Fe-NiCoHPi exhibits remarkable activity, with low overpotentials of only 206 and 257mV at current density of 15 and 100mA cm-2 . Unceasing durability over 90h is achieved, which is superior to the effective phosphate electrocatalysts. Although the applications at high current remain challenges , this work provides an approach for designing advanced OER electrocatalysts for sustainable energy devices.

Effect of mixed-valence of manganese on water oxidation activity of La1-xCaxMnO3 (0 ≤ x ≤ 1) solid solutions

The water oxidation reaction is one of the crucial process involves 4e- and 4H+ transfer, which causes a high energy barrier and makes the water-splitting process a slow kinetic reaction. Herein, we have systematically observed the water oxidation activity of La1-xCaxMnO3 (0≤ x ≤ 1) solid solutions by tuning the valence of Mn ion through selective substitution of La3+ with Ca2+. With increasing Ca concentration in La1-xCaxMnO3 solid solutions, the water oxidation activity increases up to x = 0.5 and then decreases. Mixed-valence of Mn generated due to substitution of La3+ with Ca2+, which leads to the double exchange mechanism. This could results in high electrical conduction and a faster electron transfer rate because of the rapid charge exchange between Mn3+ and Mn4+ ions, which pinpoints the reason behind the enhanced oxygen evolution activity. Our findings will be a promising way to relate the Mn mixed-valence with its catalytic activity to design and development of efficient water oxidation catalysts.

In-situ construction of porous Fe/Ni/Co-phosphide heterostructures with electron redistribution for the efficient water oxidation reaction

Electrochemical water splitting efficiency is mainly limited by the kinetically sluggish and high overpotential oxygen evolution reaction (OER) at the anode, compared to the hydrogen evolution reaction (HER) at the cathode. Substantial efforts have been carried out to overcome the above limitations. In this work, highly active porous Fe/Ni/Co-phosphide heterostructures with electron redistribution and tailored porosity have been developed for OER catalysis application. The well-developed porosity is observed by HRTEM analysis, and the XPS analysis confirms the electronic charge redistribution. The as-synthesized catalyst exhibited an extremely low overpotential of 200 mV to reach a current density of 10 mA cm−2 and 215 mV at 50 mA cm−2 in 1 M KOH with a small Tafel slope of 42 mV dec−1 benefiting from the synergistic advantages of active heterostructures together with porous nature and regulation of the electronic structure. Also, the catalyst showed steady long-term durability during the 35 h of continuous chronopotentiometry test. The catalyst showed a high faradic efficiency of 95.8%, measured by the Rotating Ring Disk Electrode (RRDE) experiment. RRDE experiment validates the evolution of oxygen from the water oxidation process. The post-TEM analysis of the catalysts suggests that the OER catalysis goes through the formation of active species like Ni(OH)2, NiOOH, FeOOH, and CoOOH. The formation of surface oxy-hydroxides and hydroxides is responsible for the excellent OER catalytic activity.

Novel synthesis of Ti–Fe2O3/MIL-53(Fe) via the in situ process for efficient photoelectrochemical water oxidation

The slow kinetics of water oxidation has become a challenge for photoelectrochemical hydrogen production. Here, a novel organic-inorganic integrated photoanode system was constructed by using MIL-53(Fe) formed during the in-situ etching process as a cocatalyst to modify Ti–Fe2O3. The photocurrent density of Ti–Fe2O3/MIL-53(Fe) reaches 2.5 mA/cm2, 10 times that of bare Ti–Fe2O3 at 1.23 V vs. RHE, and the water oxidation photocurrent onset potential shifts 105 mV negatively. Ti–Fe2O3/MIL-53(Fe) reaches 52% at 390 nm for IPCE. The excellent photoelectrochemical performance is due to iron oxide clusters boost charge separation and transfer, in-situ etching exposes more reactive sites, and the tight connection reduces interfacial resistance, which greatly accelerates the surface kinetics of Ti–Fe2O3. The in-depth understanding is provided for in-situ modification of photoanodes by metal organic frameworks in this work.

High-Density Cationic Defects Coupling with Local Alkaline-Enriched Environment for Efficient and Stable Water Oxidation.

The inferior activity and stability of non-noble metal-based electrocatalysts for oxygen evolution reaction (OER) seriously limit their practical applications in various electrochemical energy conversion systems. Here we report, a drastic nonequilibrium precipitation approach to construct a highly disordered crystal structure of layered double hydroxides as a model OER catalyst. The unconventional crystal structure contains high-density cationic defects coupled with a local alkaline-enriched environment, enabling ultrafast diffusion of OH- ions and thus avoiding the formation of a local acidic environment and dissolution of active sites during OER. An integrated experimental and theoretical study reveals that high-density cationic defects, especially di-cationic and multi-cationic defects, serve as highly active and durable catalytic sites. This work showcases a promising strategy of crystal structure engineering to construct robust active sites for high-performance oxygen evolution in an alkaline solution.

High‐Density Cationic Defects Coupling with Local Alkaline‐Enriched Environment for Efficient and Stable Water Oxidation

AbstractThe inferior activity and stability of non‐noble metal‐based electrocatalysts for oxygen evolution reaction (OER) seriously limit their practical applications in various electrochemical energy conversion systems. Here we report, a drastic nonequilibrium precipitation approach to construct a highly disordered crystal structure of layered double hydroxides as a model OER catalyst. The unconventional crystal structure contains high‐density cationic defects coupled with a local alkaline‐enriched environment, enabling ultrafast diffusion of OH− ions and thus avoiding the formation of a local acidic environment and dissolution of active sites during OER. An integrated experimental and theoretical study reveals that high‐density cationic defects, especially di‐cationic and multi‐cationic defects, serve as highly active and durable catalytic sites. This work showcases a promising strategy of crystal structure engineering to construct robust active sites for high‐performance oxygen evolution in an alkaline solution.

Ultrathin TiO2 Blocking Layers via Atomic Layer Deposition toward High-Performance Dye-Sensitized Photo-Electrosynthesis Cells

The collection of solar energy in chemical bonds via dye-sensitized photoelectrosynthesis cells (DSPECs) is a reliable solution. Herein, atomic layer deposition (ALD) introduced ultrathin blocking layers (BLs) between a mesoporous TiO2 membrane and fluorine-doped tin oxide (FTO), and much improved photoelectrochemical water oxidation performance was well documented. Samples with different BL thicknesses deposited on FTO were obtained by ALD. In the photoanode, polypyridyl Ru(II) complexes were used as photosensitizers, and Ru(bda)-type was used as a catalyst during water oxidation. Under one sun irradiation, the BL (i) increased the photocurrent density; (ii) slowed down the open-circuit voltage decay (OCVD) by electrochemical measurement; (iii) increased the photo-generated electron lifetime roughly from 1 s to more than 100 s; and (iv) enhanced the water oxidation efficiency from 25% to 85% with 0.4 V of applied voltage bias. All this pointed out that the ALD technique-prepared layers could greatly hinder the photogenerated electron–hole pair recombination in the TiO2-based photoanode. This study offers critical backing for the building of molecular films by the ALD technique to split water effectively.

Temperature-Controlled Transformation of WO3 Nanowires into Active Facets-Exposed Hexagonal Prisms toward Efficient Visible-Light-Driven Water Oxidation.

A unique transformation of WO3 nanowires (NW-WO3) into hexagonal prisms (HP-WO3) was demonstrated by tuning the temperature of the (N2H4)WO3 precursor suspension prepared from tungstic acid and hydrazine as a structure-directing agent. The precursor preparation at 20 °C followed by calcination at 550 °C produced NW-WO3 nanocrystals (ca. <100 nm width, 3-5 μm length) with anisotropic growth of monoclinic WO3 crystals to (002) and (200) planes and a polycrystalline character with randomly oriented crystallites in the lateral face of nanowires. The precursor preparation at 45 °C followed by calcination at 550 °C produced HP-WO3 nanocrystals (ca. 500-1000 nm diameter) with preferentially exposed (002) and (020) facets on the top-flat and side-rectangle surfaces, respectively, of hexagonal prismatic WO3 nanocrystals with a single-crystalline character. The HP-WO3 electrode exhibited the superior photoelectrochemical (PEC) performance for visible-light-driven water oxidation to that for the NW-WO3 electrode; the incident photon-to-current conversion efficiency (IPCE) of 47% at 420 nm and 1.23 V vs RHE for HP-WO3 was 3.1-fold higher than 15% for the NW-WO3 electrode. PEC impedance data revealed that the bulk electron transport through the NW-WO3 layer with the unidirectional nanowire structure is more efficient than that through the HP-WO3 layer with the hexagonal prismatic structure. However, the water oxidation reaction at the surface for the HP-WO3 electrode is more efficient than the NW-WO3 electrode, contributing significantly to the superior PEC water oxidation performance observed for the HP-WO3 electrode. The efficient water oxidation reaction at the surface for the HP-WO3 electrode was explained by the high surface fraction of the active (002) facet with fewer grain boundaries and defects on the surface of HP-WO3 to suppress the electron-hole recombination at the surface.

Lignosulfonate-assisted in situ synthesis of Co9S8–Ni3S2 heterojunctions encapsulated by S/N co-doped biochar for efficient water oxidation

The development of highly active and stable earth-rich electrocatalysts remains a major challenge to release the reliance on noble metal catalysts in sustainable (electro)chemical processes. In this work, metal sulfides encapsulated with S/N co-doped carbon were synthesized with a one-step pyrolysis strategy, where S was introduced during the self-assembly process of sodium lignosulfonate. Due to the precise coordination of Ni and Co ions with lignosulfonate, an intense-interacted Co9S8–Ni3S2 heterojunction was formed inside the carbon shell, causing the redistribution of electrons. An overpotential as low as 200 mV was obtained over Co9S8–Ni3S2@SNC to reach a current density of 10 mA cm−2. Only a slight increase of 14.4 mV was observed in a 50 h chronoamperometric stability test. Density functional theory (DFT) calculations showed that Co9S8–Ni3S2 heterojunctions encapsulated with S/N co-doped carbon can optimize the electronic structure, lower the reaction energy barrier, and improve the OER reaction activity. This work provides a novel strategy for constructing highly efficient and sustainable metal sulfide heterojunction catalysts with the assistance of lignosulfonate biomass.

Enhancement of charge separation and hole utilization in a Ni2P2O7-Nd-BiVO4 photoanode for efficient photoelectrochemical water oxidation

It is necessary for photoelectrochemical (PEC) water splitting to reduce the electron-hole recombination rate and enhance the water oxidation reaction kinetics. Here, we prepared Ni2P2O7-Nd-BiVO4 composite photoanodes by coupling Ni2P2O7 co-catalysts to neodymium (Nd)-doped BiVO4 surfaces through photo-assisted electrodeposition. The Ni2P2O7-Nd-BiVO4 photoanode exhibits a high photocurrent density of 3.6 mA cm−2 at 1.23 V vs reversible hydrogen electrode (RHE), which is three times higher than that of the bare BiVO4 (1.2 mA cm−2). Detailed characterizations demonstrate that Nd doping reduces the band gap, significantly increases the carrier density and effectively reduces the charge transfer resistance. More importantly, the Ni2P2O7 co-catalyst has multiple roles. Specifically, it can act as a hole extraction layer to accelerate hole migration and inhibit hole-electron recombination. At the same time, it significantly improves the water oxidation reaction kinetics. In addition, it also provides more water oxidation active sites. This work provides ideas for the design and study of efficient BiVO4-based photoanodes.

Graphene Mediates Charge Transfer between Lead Chromate and a Cobalt Cubane Cocatalyst for Photocatalytic Water Oxidation.

The interfacial barrier of charge transfer from semiconductors to cocatalysts means that the photogenerated charges cannot be fully utilized, especially for the challenging water oxidation reaction. Using cobalt cubane molecules (Co4 O4 ) as water oxidation cocatalysts, we rationally assembled partially oxidized graphene (pGO), acting as a charge-transfer mediator, on the hole-accumulating {-101} facets of lead chromate (PbCrO4 ) crystal. The assembled pGO enables preferable immobilization of Co4 O4 molecules on the {-101} facets of the PbCrO4 crystal, which is favorable for the photogenerated holes transferring from PbCrO4 to Co4 O4 molecules. The surface charge-transfer efficiency of PbCrO4 was boosted by selective assembly of pGO between PbCrO4 and Co4 O4 molecules. An apparent quantum efficiency for photocatalytic water oxidation on the Co4 O4 /pGO/PbCrO4 photocatalyst exceeded 10 % at 500 nm. This strategy of rationally assembling charge-transfer mediator provides a feasible method for acceleration of charge transfer and utilization in semiconductor photocatalysis.

Graphene Mediates Charge Transfer between Lead Chromate and a Cobalt Cubane Cocatalyst for Photocatalytic Water Oxidation

AbstractThe interfacial barrier of charge transfer from semiconductors to cocatalysts means that the photogenerated charges cannot be fully utilized, especially for the challenging water oxidation reaction. Using cobalt cubane molecules (Co4O4) as water oxidation cocatalysts, we rationally assembled partially oxidized graphene (pGO), acting as a charge‐transfer mediator, on the hole‐accumulating {−101} facets of lead chromate (PbCrO4) crystal. The assembled pGO enables preferable immobilization of Co4O4 molecules on the {−101} facets of the PbCrO4 crystal, which is favorable for the photogenerated holes transferring from PbCrO4 to Co4O4 molecules. The surface charge‐transfer efficiency of PbCrO4 was boosted by selective assembly of pGO between PbCrO4 and Co4O4 molecules. An apparent quantum efficiency for photocatalytic water oxidation on the Co4O4/pGO/PbCrO4 photocatalyst exceeded 10 % at 500 nm. This strategy of rationally assembling charge‐transfer mediator provides a feasible method for acceleration of charge transfer and utilization in semiconductor photocatalysis.

One-Step High-Temperature Electrodeposition of Fe-Based Films as Efficient Water Oxidation Catalysts

Electrolysis of water to produce hydrogen requires an efficient catalyst preferably made of cheap and abundant metal ions for the improved water oxidation reaction. An Fe-based film has been deposited in a single step by electrochemical deposition at temperatures higher than the room temperature. Until now, the electrodeposition of iron oxide has been carried out at 298 K or at lower temperatures under a controlled atmosphere to prohibit atmospheric oxidation of Fe2+ of the iron precursor. A metal inorganic complex, ferrocene, and non-aqueous electrolyte medium propylene carbonate have been used to achieve electrodeposition of iron oxide without the need of any inert or controlled atmosphere. At 298 K, the amorphous film was formed, whereas at 313 K and at higher temperatures, the hematite film was grown, as confirmed by X-ray diffraction. The transformation of iron of the ferrocene into a higher oxidation state under the experimental conditions used was further confirmed by X-ray photoelectron spectroscopy, ultraviolet-visible, and electron paramagnetic resonance spectroscopic methods. The films deposited at 313 K showed the best performance for water oxidation with remarkable long-term electrocatalytic stability and an impressive turnover frequency of 0.028 s-1 which was 4.5 times higher than that of films deposited at 298 K (0.006 s-1). The observed overpotential to achieve a current density of 10 mA cm-2 was found to be 100 mV less for the film deposited at 313 K compared to room-temperature-derived films under similar experimental conditions. Furthermore, electrochemical impedance data revealed that films obtained at 313 K have the least charge transfer resistance (114 Ω) among all, supporting the most efficient electron transport in the film. To the best of our knowledge, this is the first-ever report where the crystalline iron-based film has been shown to be electrodeposited without any post-deposition additional treatment for alkaline oxygen evolution reaction application.

Two-Dimensional Sb Modified TiO2 Nanorod Arrays as Photoanodes for Efficient Solar Water Splitting.

As one of the widely studied semiconductor materials, titanium dioxide (TiO2) exhibits high photoelectrochemical (PEC) water-splitting performance as well as high chemical and photo stability. However, limited by a wide band gap and fast electron-hole recombination rate, the low solar-to-hydrogen conversion efficiency remains a bottleneck for the practical application of TiO2-based photoelectrodes. To improve the charge separation and water oxidation efficiency of TiO2 photoanodes, antimonene, a two-dimensional (2D) material obtained by liquid-phase exfoliation, was assembled onto TiO2 nanorod arrays (TNRAs) by a simple drop-coating assembly process. PEC measurements showed that the resulting 2D Sb/TiO2 photoelectrode displayed an enhanced photocurrent density of about 1.32 mA cm-2 in 1.0 M KOH at 0.3 V vs. Hg/HgO, which is ~1.65 times higher than that of the pristine TNRAs. Through UV-Vis absorption and electrochemical impedance spectroscopy measurements, it was possible to ascribe the enhanced PEC performances of the 2D Sb/TiO2 photoanode to increased absorption intensity in the visible light region, and improved interfacial charge-transfer kinetics in the 2D Sb/TiO2 heterojunction, which promotes electron-hole separation, transfer, and collection.

Atomically dispersed Ru oxide catalyst with lattice oxygen participation for efficient acidic water oxidation

Atomically dispersed Ru oxide catalyst with lattice oxygen participation for efficient acidic water oxidation

Photosystem II Inspired NiFe-Based Electrocatalysts for Efficient Water Oxidation via Second Coordination Sphere Effect.

The mismatched fast-electron-slow-proton process in the electrocatalytic oxygen evolution reaction (OER) severely restricts the catalytic efficiency. To overcome these issues, accelerating the proton transfer and elucidating the kinetic mechanism are highly sought after. Herein, inspired by photosystem II, we develop a family of OER electrocatalysts with FeO6 /NiO6 units and carboxylate anions (TA2- ) in the first and second coordination sphere, respectively. Benefiting from the synergistic effect of the metal units and TA2- , the optimized catalyst delivers superior activity with a low overpotential of 270 mV at 200 mA cm-2 and excellent cycling stability over 300 h. A proton-transfer-promotion mechanism is proposed by in situ Raman, catalytic tests, and theoretical calculations. The TA2- (proton acceptor) can mediate proton transfer pathways by preferentially accepting protons, which optimizes the O-H adsorption/activation process and reduces the kinetic barrier for O-O bond formation.