Stable Water Oxidation Research Articles

Iron-Induced Localized Oxide Path Mechanism Enables Efficient and Stable Water Oxidation.

The sluggish reaction kinetics of the anodic oxygen evolution reaction (OER) and the inadequate catalytic performance of non-noble metal-based electrocatalysts represent substantial barriers to the development of anion exchange membrane water electrolyzer (AEMWE). This study performed the synthesis of a three-dimensional (3D) nanoflower-like electrocatalyst (CFMO) via a simple one-step method. The substitution of Co with Fe in the structure induces a localized oxide path mechanism (LOPM), facilitating direct O-O radical coupling for enhanced O2 evolution. The optimized CFMO-2 electrocatalyst demonstrates superior OER performance, achieving an overpotential of 217 mV at 10 mA cm-2, alongside exceptional long-term stability with minimal degradation after 1000 h of operation in 1.0 M KOH. These properties surpass most of conventional noble metal-based electrocatalysts. Furthermore, the assembled AEMWE system, utilizing CFMO-2, operates with a cell voltage of 1.65 V to deliver 1.0 A cm-2. In situ characterizations reveal that, in addition to the traditional adsorbate evolution mechanism (AEM) at isolated Co sites, a new LOPM occurred around the Fe and Co bimetallic sites. First-principles calculations confirm the LOPM greatly reduced the energy barriers. This work highlights the potential of LOPM for improving the design of non-noble metal-based electrocatalysts and the development of AEMWE.

Iron‐Induced Localized Oxide Path Mechanism Enables Efficient and Stable Water Oxidation

The sluggish reaction kinetics of the anodic oxygen evolution reaction (OER) and the inadequate catalytic performance of non‐noble metal‐based electrocatalysts represent substantial barriers to the development of anion exchange membrane water electrolyzer (AEMWE). This study performed the synthesis of a three‐dimensional (3D) nanoflower‐like electrocatalyst (CFMO) via a simple one‐step method. The substitution of Co with Fe in the structure induces a localized oxide path mechanism (LOPM), facilitating direct O–O radical coupling for enhanced O2 evolution. The optimized CFMO‐2 electrocatalyst demonstrates superior OER performance, achieving an overpotential of 217 mV at 10 mA cm–2, alongside exceptional long‐term stability with minimal degradation after 1000 h of operation in 1.0 M KOH. These properties surpass most of conventional noble metal‐based electrocatalysts. Furthermore, the assembled AEMWE system, utilizing CFMO‐2, operates with a cell voltage of 1.65 V to deliver 1.0 A cm–2. In situ characterizations reveal that, in addition to the traditional adsorbate evolution mechanism (AEM) at isolated Co sites, a new LOPM occurred around the Fe and Co bimetallic sites. First‐principles calculations confirm the LOPM greatly reduced the energy barriers. This work highlights the potential of LOPM for improving the design of non‐noble metal‐based electrocatalysts and the development of AEMWE.

Bond engineering: weakening Ru–O covalency for efficient and stable water oxidation in acidic solutions

The persistent stability of ruthenium dioxide (RuO2) in acidic oxygen evolution reactions (OER) is compromised by the involvement of lattice oxygen (LO) and metal dissolution during the OER process. Heteroatom doping has been recognized as a viable strategy to foster the stability of RuO2 for acidic OER applications. This study presented an ion that does not readily gain or lose electrons, Ba2+, into RuO2 (Ba–RuO2) nanosheet (NS) catalyst that increased the number of exposed active sites, achieving a current density of 10 mA/cm2 with an overpotential of only 229 mV and sustaining this output for over 250 h. According to density functional theory (DFT) and X-ray absorption spectroscopy, Ba doping resulted in a longer Ru–O bond length, which in turn diminished the covalency of the bond. This alteration curtailed the involvement of LO and the dissolution of ruthenium (Ru), thereby markedly improving the durability of the catalyst over extended periods. Additionally, attenuated total reflectance-surface enhanced infrared absorption spectroscopy analysis substantiated that the OER mechanism shifted from a LO-mediated pathway to an adsorbate evolution pathway due to Ba doping, thereby circumventing Ru over-oxidation and further enhancing the stability of RuO2. Furthermore, DFT findings uncovered that Ba doping optimizes the adsorption energy of intermediates, thus enhancing the OER activity in acidic environments. This study offers a potent strategy to guide future developments on Ru-based oxide catalysts’ stability in an acidic environment.

TiO2 modified NiFe-LDH as photoanode to achieve high efficiency photochemical water oxidation reaction

With the semiconductor modified oxygen evolution (OER) catalyst as the photoanode, the solar energy can be fully utilized, and the synergistic reaction makes the OER catalyst play a great role in the photochemical (PEC) water decomposition. Herein, we adopted a one-step hydrothermal method to introduce TiO2 to form heterojunction as photoanode in a well-known NiFe-LDH electrocatalyst, which contributes to carrier separation and transfer efficiency, thereby speeding up the water oxidation reaction kinetics. Benefiting from the TiO2/Ni4Fe6-LDH heterojunctions, the TiO2/ Ni4Fe6-LDH shows an overpotential of 371 mV @30 mA cm−2 and a Tafel slope of 131.36 mV/dec under illumination, which is better than Ni4Fe6-LDH and TiO2. The comparison experiment of oxygen evolution efficiency showed that the polarization current density of TiO2/Ni4Fe6-LDH reached 12 mA cm−2 under the illumination voltage of 1.72 V, which was twice the current density under the non-illumination condition. Surface electronic structure analysis shows that these excellent OER performance are largely due to the introduction of TiO2, which not only enables Ni4Fe6-LDH surface to have more oxygen vacancy, increase photoanode conductivity and accelerate reaction electron conduction, but also accelerates hole capture and enhances OER reaction kinetics. This synergistic effect between semiconductor and OER catalyst provides more ideas for realizing efficient and stable photoelectrochemical water oxidation.

Selenate oxyanion-intercalated NiFeOOH for stable water oxidation via lattice oxygen oxidation mechanism

Transition metal-based compounds can serve as pre-catalysts to obtain genuine oxygen evolution reaction (OER) electrocatalysts in the form of oxyhydroxides through electrochemical activation. However, the role and existence form of leached oxygen anions are still controversial. Herein, we selected iron selenite-wrapped hydrated nickel molybdate (denoted as NiMoO/FeSeO) as a pre-catalyst to study the oxyanion effect. It is surprising to find that SeO42− exists in the catalyst in the form of intercalation, which is different from previous studies that suggest that anions are doped with residual elements after electrochemical activation, or adsorbed on the catalyst surface. The experiment and theoretical calculations show that the existence of SeO42− intercalation effectively adjusts the electronic structure of NiFeOOH, promotes intramolecular electron transfer and O–O release, and thus lowers the reaction energy barrier. As expected, the synthesized NiFeOOH-SeO only needs 202 and 285 mV to attain 100 and 1000 mA cm−2 in 1 M KOH. Further, the anion exchange membrane water electrolyzer (AEMWE) consisting of NiFeOOH-SeO anode and Pt/C cathode can reach 1 A cm−2 at 1.70 V and no significant attenuation within 300 h. Our findings provide insights into the mechanism, by which the intercalated oxyanions enhance the OER performance of NiFeOOH, thereby facilitating large-scale hydrogen production through AEMWE.

Textured RuIrAgMnO2 Oxides With Preferentially Orientated (110) Facet by Concerted Shaping of Ag and Mn for Stable Acid Water Oxidation

Textured RuIrAgMnO₂ Oxides With Preferentially Orientated (110) Facet by Concerted Shaping of Ag and Mn for Stable Acid Water Oxidation

Strong interaction heterointerface of NiFe oxyhydroxide/cerium oxide for efficient and stable water oxidation

NiFe oxyhydroxides (NiFeOxHy) are the benchmark catalysts for alkaline oxygen evolution reaction (OER), however, it is still challenging for these electrocatalysts to achieve both high activity and long-term stability. Herein, we demonstrate that strong interaction heterointerface of NiFeOxHy/cerium oxide (CeO2) can control the reconstruction process of NiFeOxHy and the reaction pathway of OER, which simultaneously improves the activity and stability of the catalyst. Interestingly, after electrochemical activation, with and without CeO2, NiFeOxHy oxyhydroxides exhibit completely different structures, with the former being uniformly distributed ultrafine nanosheets and the latter being spherical agglomerates of larger sized nanosheets. The strong heterointerface interaction induces the electrons of Ni and Fe to shift to Ce. The optimized catalyst exhibits a low overpotential of 240 mV at 100 mA cm−2 with the durability over 2000 h at 200 mA cm−2. The OER mechanism studies indicate that NiFeOxHy/CeO2 heterointerface follows lattice oxygen oxidation mechanism with accelerated kinetics.

Fe,Ce Co-Doped Ni3S2/NiS Polymorphism Nanosheets with Improved Electrocatalytic Activity and Stability for Water Oxidation.

Balancing the relationship between electrocatalytic activity and stability of sulfide catalysts during oxygen evolution reaction (OER) has been attracting extensive research interest. Here, a simple electrodeposition-vulcanization two-step route was designed to successfully construct nickel foam supported sheet-like Fe,Ce-codoped Ni3S2/NiS polymorphism catalyst (labeled as Fe,Ce-Ni3S2/NiS/NF). Electrochemical measurements showed that the as-obtained Fe,Ce-Ni3S2/NiS/NF electrode presented excellent OER electrocatalytic performances. In 1 M KOH solution, merely 173 and 234 mV of overpotentials were required to deliver the current densities of 10 and 100 mA cm-2, respectively. Further investigations revealed that the Fe,Ce co-doping regulated the electron density around Ni, which promoted the conversion of Ni towards the higher valence state and simultaneously, avoided the stability decrease of the catalyst caused by excessive oxidation corrosion. Moreover, the defects generated during vulcanization also contributed to promoting water oxidation. The present work provides a facile and feasible approach to balance the relationship between the stability and the activity of sulfide catalysts for OER.

Grain Boundary Defect Engineering in Rutile Iridium Oxide Boosts Efficient and Stable Acidic Water Oxidation.

Proton exchange membrane water electrolysis (PEMWE) is considered a promising technology for coupling with renewable energy sources to achieve clean hydrogen production. However, constrained by the sluggish kinetics of the anodic oxygen evolution reaction (OER) and the acidic abominable environment render the grand challenges in developing the active and stable OER electrocatalyst, leading to low efficiency of PEMWE. Herein, we develop the rutile-type IrO2 nanoparticles with abundant grain boundaries and the continuous nanostructure through the joule heating and sacrificial template method. The optimal candidate (350-IrO2) demonstrates remarkable electrocatalytic activity and stability during the OER, presenting a promising advancement for efficient PEMWE. DFT calculations verified that grain boundaries can modulate the electronic structure of Ir sites and optimize the adsorption of oxygen intermediates, resulting in the accelerated kinetics. 350-IrO2 affords a rapid OER process with 20 times higher mass activity (0.61 A mgIr -1) than the commercial IrO2 at 1.50 V vs. RHE. Benefiting from the reduced overpotential and the preservation of the stable rutile structure, 350-IrO2 exhibits the stability of 200 h test at 10 mA cm-2 with only trace decay of 11.8 mV. Moreover, the assembled PEMWE with anode 350-IrO2 catalyst outputs the current density up to 2 A cm-2 with only 1.84 V applied voltage, long-term operation for 100 h without obvious performance degradation at 1 A cm-2.

CoFe hydroxide towards CoP2-FeP4 heterojunction for efficient and long-term stable water oxidation

Electrochemical water splitting stands out as a promising avenue for green hydrogen production, yet its efficiency is fundamentally governed by the oxygen evolution reaction (OER). In this work, we investigated the growth mechanism of CoFe hydroxide formed by in situ self-corrosion of iron foam for the first time and the significant influence of dissolved oxygen in the immersion solution on this process. Based on this, the CoP2-FeP4/IF heterostructure catalytic electrode demonstrates exceptional OER activity in a 1 M KOH electrolyte, with an overpotential of only 253 ± 4 mV (@10 mA cm−2), along with durability exceeding 1000 h. Density functional theory calculations indicate that constructing heterojunction interfaces promotes the redistribution of interface electrons, optimizing the free energy of adsorbed intermediate during the water oxidation process. This research highlights the importance of integrating self-corroding in-situ growth with interface engineering techniques to develop efficient water splitting materials.

Bioinspired Tetranuclear Manganese Cubane Complex as an Efficient Molecular Electrocatalyst for Two-Electron Water Oxidation Towards Hydrogen Peroxide.

Stable homogeneous two-electron water oxidation electrocatalysts are highly demanded to understand the precise mechanism and reaction intermediates of electrochemical H2O2 production. Here we report a tetranuclear manganese complex with a cubane structure which can electrocatalyze water oxidation to hydrogen peroxide under alkaline and neutral conditions. Such a complex demonstrates an optimal Faradaic efficiency (FE) of 87 %, which is amongst (if not) the highest FE(H2O2) of reported homogeneous and heterogeneous electrocatalysts. In addition, active species were identified and co-catalysts were excluded through ESI-MS characterization. Furthermore, we identified water binding sites and isolated one-electron oxidation intermediate by chemical oxidation of the catalyst in the presence of water substrates. It is evident that efficient proton-accepting electrolytes avoid rapid proton building-up at electrode and substantially improve reaction rate and selectivity. Accordingly, we propose a two-electron catalytic cycle model for water oxidation to hydrogen peroxide with the bioinspired molecular electrocatalyst. The present work is expected to provide an ideal platform to elucidate the two-electron WOR mechanism at the atomic level.

Surface reconstruction of ruddlesden–popper-based oxides in nonreactive environments and under electrochemical conditions for the oxygen evolution reaction

Perovskite oxides have emerged as catalysts for electrochemical water splitting, and surface reconstruction is crucial for their electrocatalytic performance. In this study, we report the surface reconstruction of Ruddlesden–Popper-based oxides under nonreactive and electrochemical conditions. The rapid migration of Sr ions from the bulk to the surface results in a porous structure, increase the number of oxygen vacancies, and produces an A-site cation deficiency. Collectively, these modifications significantly enhance the electrocatalytic activity and stability for water oxidation. In addition, the engineered electrocatalysts have a low overpotential of 350 mV at 10 mA cm−2, alone with a Tafel slope of 77 mV dec−1. They also exhibit outstanding durability, maintaining a current density of 5 mA cm−2 over 6 h.

Unveiling the multiple effects of MOF-derived TiO2 on Ti-Fe2O3 photoanodes for efficient and stable photoelectrochemical water oxidation

Unveiling the multiple effects of MOF-derived TiO2 on Ti-Fe2O3 photoanodes for efficient and stable photoelectrochemical water oxidation

Simultaneous enhancement of charge transfer and surface catalysis through a polymetallic oxide cocatalyst on BiVO4 photoanodes for highly efficient and stable water oxidation

The rate-determining oxygen evolution reaction (OER) always limits the high-efficient conversion of solar energy to green hydrogen fuels through photoelectrocatalytic or photocatalytic water splitting. The high catalytic overpotential and the instability of catalytic center are commonly regarded as the primary factors contributing to the low rate of OER, remaining to be a challenge in the field of water splitting. Herein, a polymetallic oxide cocatalyst (Mo-MnOy/FeCoNiOx) with well-defined electronic and catalytic properties is designed on BiVO4 photoelectrode for highly efficient and stable photoelectrocatalytic water oxidation. The experimental characterization demonstrates that the dual-layer design of Mo-MnOy/FeCoNiOx can significantly optimizes the electronic property of MnOy and FeCoNiOx components, boosting the photogenerated charge transfer between Mo-MnOy/FeCoNiOx cocatalyst and BiVO4 photoelectrode. The density functional theory (DFT) simulation reveals that the Mo sites in Mo-MnOy layer can activate the neighboring surface Mn sites instead of directly serving as the catalytic center, thereby establishing these Mn sites as primary active centers for achieving stable OER. The developed Mo-MnOy/FeCoNiOx/BiVO4 photoelectrode exhibits a current density of 6.18 mA cm−2 with an excellent stability for 30 h at 1.23 VRHE under 1 sun irradiation, exhibiting the excellent activity and durability. This work sheds light on design of high-performance multiple-component water-oxidation cocatalyst on photoanode.

Strain‐modulated Ru‐O Covalency in Ru‐Sn Oxide Enabling Efficient and Stable Water Oxidation in Acidic Solution

AbstractRuO2 is one of the benchmark electrocatalysts used as the anode material in proton exchange membrane water electrolyser. However, its long‐term stability is compromised due to the participation of lattice oxygen and metal dissolution during oxygen evolution reaction (OER). In this work, weakened covalency of Ru−O bond was tailored by introducing tensile strain to RuO6 octahedrons in a binary Ru−Sn oxide matrix, prohibiting the participation of lattice oxygen and the dissolution of Ru, thereby significantly improving the long‐term stability. Moreover, the tensile strain also optimized the adsorption energy of intermediates and boosted the OER activity. Remarkably, the RuSnOx electrocatalyst exhibited excellent OER activity in 0.1 M HClO4 and required merely 184 mV overpotential at a current density of 10 mA cm−2. Moreover, it delivered a current density of 10 mA cm−2 for at least 150 h with negligible potential increase. This work exemplifies an effective strategy for engineering Ru‐based catalysts with extraordinary performance toward water splitting.

Strain-modulated Ru-O Covalency in Ru-Sn Oxide Enabling Efficient and Stable Water Oxidation in Acidic Solution.

RuO2 is one of the benchmark electrocatalysts used as the anode material in proton exchange membrane water electrolyser. However, its long-term stability is compromised due to the participation of lattice oxygen and metal dissolution during oxygen evolution reaction (OER). In this work, weakened covalency of Ru-O bond was tailored by introducing tensile strain to RuO6 octahedrons in a binary Ru-Sn oxide matrix, prohibiting the participation of lattice oxygen and the dissolution of Ru, thereby significantly improving the long-term stability. Moreover, the tensile strain also optimized the adsorption energy of intermediates and boosted the OER activity. Remarkably, the RuSnOx electrocatalyst exhibited excellent OER activity in 0.1 M HClO4 and required merely 184 mV overpotential at a current density of 10 mA cm-2 . Moreover, it delivered a current density of 10 mA cm-2 for at least 150 h with negligible potential increase. This work exemplifies an effective strategy for engineering Ru-based catalysts with extraordinary performance toward water splitting.

A dye sensitized photosynthesis cell for stable water oxidation mediated by photo-generated bromine.

The critical step of a dye-sensitized photoelectrochemical cell (DSPEC) is water oxidation. The photoanodes suffer rapid surface carrier recombination due to slow water oxidation kinetics and this results in low solar conversion efficiency and poor stability. Here, we design a novel sensitization-oxidation photo-anode, where the [Ru(4,4'-PO3H2-bpy)(bpy)2]2+ (RuP2+, bpy = 2,2'-bipyridine) chromophore and [Ru(bda)(pic)2] (pic = picoline, bda = 2,2'-bipyridine-6,6'-dicarboxylate) water oxidation catalyst (WOC) are immobilized separately on the surface of a mesoporous semiconductor thin film. The electrode creates a mobile and strong Br3- oxidant generated by the dye-sensitized electrode, which initiates water oxidation at a remote catalytic site. Under 100 mW cm-2 illumination in pH 4.65 in 0.1 M acetate buffer solution, the photoanode could perform a stable photoelectrochemical water oxidation for 6 hours with a photocurrent density of around 0.25 mA cm-2. This dual electrode could open a new door by utilizing an electron transfer mediator to design highly stable photoelectrochemical cells.

(Invited) Acid Stable Water Oxidation Catalysts for PEM Water Electrolysis

Water electrolysis is a promising method to produce hydrogen from renewable electricity. However, the development of 3d metal catalysts for the oxygen evolution reaction (OER) is a critical challenge, especially in the case of polymer electrolyte membrane (PEM) electrolyzers, which are considered to be one of the most efficient electrolysis systems. The scarcity of iridium required for these systems prevents their widespread deployment at the global terawatt scale, and therefore the development of alternative catalysts has been highlighted as a real bottleneck for water electrolysis.In this talk, I will report on how the incorporation of Mn into the Co3O4 spinel lattice can result in a two order of magnitude increase in stability without compromising activity (1, 2). I will also report on how the lifetime of Mn-based catalysts in acid can be extended by modulating the lattice oxygen structure (3). Finally, I will discuss the performance of Mn-based OER catalysis under the actual conditions of PEM water electrolysis (3).(1) A. Li, S. Kong, C. Guo, H. Ooka, K. Adachi, D. Hashizume, Q. Jiang, H. Han, J. Xiao, R. Nakamura, Enhancing the stability of cobalt spinel oxide towards sustainable oxygen evolution in acid, Nat. Catal., 2022, 5, 109-118, DOI: 10.1038/s41929-021-00732-9(2) A. Li, H. Ooka, N. Bonnet, T. Hayashi, Y. Sun, Q. Jiang, C. Li, H. Han, R. Nakamura, Stable potential windows for long-term electrocatalysis by manganese oxides under acidic conditions, Angew. Chem., Int. Ed., 2019, 58, 5054-5058. DOI: 10.1002/anie.201813361(3) S. Kong, et al (under review)

Construction of Pd-doped RuO2 nanosheets for efficient and stable acidic water oxidation

RuO2 has been considered a potential alternative to commercial IrO2 for the oxygen evolution reaction (OER) due to its superior intrinsic activity. However, its inherent structure dissolution in acidic environments restricts its commercial applications. In this study, we report a novel Pd-doped ruthenium oxide (Pd–RuO2) nanosheet catalyst that exhibits improved activity and stability through a synergistic effect of Pd modulation of Ru electronic structure and the two-dimensional structure. The catalyst exhibits excellent performance, achieving an overpotential of only 204 mV at a current density of 10 mA cm−2. Impressively, after undergoing 8000 cycles of cyclic voltammetry testing, the overpotential merely decreased by 5 mV. The PEM electrolyzer with Pd0.08Ru0.92O2 as an anode catalyst survived an almost 130 h operation at 200 mA cm−2. To elucidate the underlying mechanisms responsible for the enhanced stability, we conducted an X-ray photoelectron spectroscopy (XPS) analysis, which reveals that the electron transfer from Pd to Ru effectively circumvents the over-oxidation of Ru, thus playing a crucial role in enhancing the catalyst's stability. Furthermore, density functional theory (DFT) calculations provide compelling evidence that the introduction of Pd into RuO2 effectively modulates electron correlations and facilitates the electron transfer from Pd to Ru, thereby preventing the over-oxidation of Ru. Additionally, the application of the two-dimensional structure effectively inhibited the aggregation and growth of nanoparticles, further bolstering the structural integrity of the catalyst.

In-situ reconstruction of rock-like 3D hierarchical MIL-53(Fe) self-supporting electrode with oxygen vacancy induced ultra-long stable and efficient water oxidation

The exploitation of efficient, stable and cheap electrocatalyst for oxygen evolution reaction (OER) is very significant to the development of energy technology. In this study, Fe-based metal–organic frameworks (MIL-53(Fe)) self-supporting electrode with a 3D hierarchical open structure was developed through a semi-sacrificial strategy. The self-supporting electrode exhibits an excellent OER performance with an overpotential of 328 mV at 100 mA cm−2 in 1 M KOH, which is superior than that of IrO2 catalyst. Importantly, the optimized self-supporting electrode could operate at 100 mA cm−2 for 520 h without visible decrease in activity. It was also found that the structure of MIL-53(Fe) was in-situ self-reconstructed into oxyhydroxides during OER process. However, the 3D hierarchical open structure assembled with nano-microstructures kept well, which ensured the long-term stability of our self-supporting electrode for OER. Furthermore, density functional theory (DFT) calculations reveal that the FeOOH with rich oxygen vacancy transformed from MIL-53(Fe) plays a key role for the OER catalytic activity. And, the uninterrupted formation of oxygen vacancy during OER process ensures the continuous OER catalytic activity, which is the original source for the ultra-long stability of the self-supporting electrode toward OER. This work explores the way for the construction of efficient self-supporting oxygen electrodes based on MOFs.