Water Oxidation Research Articles

Structurally Locked High-Crystalline Covalent Triazine Frameworks Enable Remarkable Overall Photosynthesis of Hydrogen Peroxide.

The development of green and efficient hydrogen peroxide (H2O2) production is of great interest but remains challenging. Herein, we develop a new and simple strategy via locking the coplanarity in highly crystalline covalent triazine frameworks (CTFs) to remarkably boost direct photosynthesis of H2O2 from oxygen and water. The exfoliated ultrathin 2D-CTF nanosheets exhibit excellent photocatalytic H2O2 evolution with an ultrahigh solar-to-chemical efficiency of 0.91% and a superb apparent quantum yield of 16.8% at 420 nm, surpassing all previous CTFs and most of the metal-free photocatalysts ever reported. Our detailed experimental and theoretical studies reveal that the spatially locked structure in the crystalline CTF photocatalyst can not only greatly enhance the separation and transfer of photoexcited charge-carriers for promoting H2O2 photogeneration but also alter the local electronic structures that unexpectedly turn water oxidation from a four-electron route to a two-electron pathway, resulting in a 100% atom utilization efficiency. This work provides valuable insights into the designed synthesis of highly efficient metal-free photocatalysts and precise control over photocatalytic reaction pathways in organic materials.

Heat transfer enhancement using ternary hybrid nanofluid for cross-viscosity model with intelligent Levenberg-Marquardt neural networks approach incorporating entropy generation

Thermal heat transfer analysis of trihybrid nanofluids using an intelligent Levenberg-Marquardt neural network (ANN-LMA) approach, with a focus on entropy generation, has been conducted. The flow equations were modeled in Cartesian coordinates and simplified using dimensionless variables. Partial differential equations were converted into ordinary differential equations through appropriate similarity transformations. These ordinary differential equations were then solved using the finite element method applied to a data set evaluated from (ANN-LMA) approach. This dataset can be input into MATLAB to generate predicted solutions for flow patterns. The ANN-LMA technique was employed to evaluate the efficiency of heat transfer characteristics for nanofluids in various scenarios. Incorporating carbon nanotubes (both single-wall (SWCNT) and multi-wall (MWCNT)) along with iron oxide in water, the study demonstrates their effectiveness in enhancing heat transfer. These nanofluids have broad industrial applications, such as in coolant enhancement, cancer therapy, and solar radiation management, and show promising results. This study specifically examines the flow properties of water-based CNT cross-trihybrid nanofluids over a convectively heated surface, leveraging their unique characteristics. Improvements in heat transfer are achieved through the introduction of dissipative heat, thermal radiation, and external heat sources or sinks. The performance of the computational solver was assessed using error histograms, regression analyses, and Mean Squared Error (MSE) results. The physical significance of the designed factors is graphically depicted and discussed in detail. It was found that radiative heat increases surface heat energy through substantial accumulation, thereby enhancing heat transfer properties, while dissipative heat, due to Joule dissipation and other external sources, significantly raises the fluid temperature.

Frustrated Lewis Pair-Promoted Organocatalytic Transformation of Hydrosilanes into Silanols with Water Oxidant.

Owing to their unique properties, the silanols have attracted intense attention but remain challenging to prepare from the organocatalytic oxidation of hydrosilanes using H2O as a green oxidant. Herein, we employ a frustrated Lewis pair (FLP) to successfully suppress the formation of undesired siloxanes and produce silanols in high to excellent yields in the presence of H2O. Mechanistic studies suggest that the reaction is initiated with the activation of FLP by H2O rather than by silanes and goes through a concerted SN2 mechanism. More importantly, the combination of the FLP-catalyzed oxidation of hydrosilanes with B(C6F5)3-catalyzed dehydrogenation enables us to realize the precise synthesis of sequence-controlled oligosiloxanes. This method exhibits a broad substrate scope and can be easily scaled up, thus exhibiting promising application potentials in the precision synthesis of silicon-containing polymer materials.

Interface Synergistic Effect of NiFe-LDH/3D GA Composites on Efficient Electrocatalytic Water Oxidation.

Currently, NiFe-LDH exhibits an excellent oxygen evolution reaction (OER) due to the interaction of the two metal elements on the layered double hydroxide (LDH) platform. However, such interaction is still insufficient to compensate for its poor electrical conductivity, limited number of active sites and sluggish dynamics. Herein, a feasible two-step hydrothermal strategy that involves coupling low-conductivity NiFe-LDH with 3D porous graphene aerogel (GA) is proposed. The optimized NiFe-LDH/GA (1:1) produced possesses a 257 mV (10 mA cm-2) overpotential and could operate stably for 56 h in an OER. Our investigation demonstrates that the NiFe-LDH/GA has a three-dimensional mesoporous structure, and that there is synergistic interaction between LDH and GA and interfacial reconstruction of NiOOH. Such an interface synergistic coupling effect promotes fast mass transfer and facilitates OER kinetics, and this work offers new insights into designing efficient and stable GA-based electrocatalysts.

Functionalized Modification of Conjugated Porous Polymers for Full Reaction Photosynthesis of H2O2

AbstractModulating the molecular structure to achieve the full reaction including oxygen reduction reaction and water oxidation reaction is a promising strategy for efficient photosynthesis of hydrogen peroxide (H2O2) but remains a challenge. Herein, a triphenylamine and naphthalimide‐based conjugated porous polymers are synthesized with photo oxidation‐reduction structures, then sulfonate (─SO3H) and quaternary ammonium groups are introduced via a post‐modification strategy to produce two photocatalysts named NI‐TPA‐NI‐SO3H and NI‐TPA‐NI‐N, respectively. Introducing charged functional groups has improved the hydrophilicity and oxygen (O2) adsorption, beyond that, the ─SO3H further stabilizes the adsorbed O2 via hydrogen bonding as well as accelerates the photogenerated carrier separation and electron/proton transport that enables full reaction photosynthesis of H2O2. Therefore, motivated by efficient charge separation, stabilized O2 adsorption, and boosted proton‐coupled electron transfer, NI‐TPA‐NI‐SO3H exhibits the highest light‐driven H2O2 production rate among the three photocatalysts, reaching 3.40 mmol g−1 h−1, which is 4.9‐fold of NI‐TPA‐NI. Remarkably, in the presence of ethylenediaminetetraacetic acid disodium salt, its rate significantly enhances to 14.5 mmol g−1 h−1, superior to most reported organic photocatalysts to the best of the knowledge.

Solar Fuel Synthesis Using a Semiartificial Colloidal Z-Scheme.

The integration of enzymes with semiconductor light absorbers in semiartificial photosynthetic assemblies offers an emerging strategy for solar fuel production. However, such colloidal biohybrid systems rely currently on sacrificial reagents, and semiconductor-enzyme powder systems that couple fuel production to water oxidation are therefore needed to mimic an overall photosynthetic reaction. Here, we present a Z-scheme colloidal enzyme system that produces fuel with electrons sourced from water. This "closed-cycle" semiartificial approach utilizes particulate SrTiO3:La,Rh and BiVO4:Mo (light absorbers), hydrogenase or formate dehydrogenase (cocatalyst), and a molecular cobalt complex (a redox mediator). Under simulated solar irradiation, this system continuously generates molecular hydrogen or formate, while co-producing molecular oxygen for 10 h using only sunlight, water, and carbon dioxide as inputs. In-depth analysis using quartz crystal microbalance, photoelectrochemical impedance spectroscopy, transient photocurrent spectroscopy, and intensity-modulated photovoltage spectroscopy provides mechanistic understanding and characterization of the semiconductor-enzyme hybrid interface. This study provides a rational platform to assemble functional semiartificial colloidal Z-scheme systems for solar fuel synthesis.

The Feasibility of Using Electrostatic Interactions for Immobilizing Ru-bda Catalysts in Covalent Organic Framework: A Proof-of-concept.

Heterogenetization of molecular catalysts effectively resolves the separation issues of homogeneous catalysts and expands their application scenarios. In recent years, more and more studies have been using non-covalent interactions to achieve the heterogenization of molecular catalysts. Herein, electrostatic attraction was used to immobilize molecular catalysts, Ru-bda small molecular catalysts in COF materials, where the charged Ru-bda catalysts were immobilized in the oppositely charged COF with a high [Ru] loading content of ~0.2 mmol [Ru] g-1 COF. The leakage experiment verified that the immobilization of Ru-bda catalysts in COF by electrostatic interactions is stable in 0.1 M HClO4 and less than 5% of molecular Ru-bda catalysts were leached into the solution in 2 hours. The chemical water oxidation experiment was conducted as a model catalysis reaction to verify the feasibility of using electrostatic interactions for immobilizing Ru-bda catalysts in COFs. The prepared Ru(bda)@COFs demonstrate a high catalytic activity of 268 μmol L-1 s-1 O2 for chemical water oxidation, illustrating the electrostatic attractions between COF and small molecules that can be used to immobilize homogeneous catalysts in heterogeneous materials. However, the robustness of COF material itself under catalytic conditions should be considered in practical applications.

Magneto-electrochemical water splitting performance of graphene oxide/nickel aluminum-layered double hydroxide nanocomposites

Designing efficient, cheap catalysts for oxygen production is very important for water electrolysis and green hydrogen production. Here, synthesis and electrocatalytic performance of graphene oxide (GO)/nickel-aluminum layered double hydroxide (NiAl-LDH) composites were investigated for water-splitting applications. The composition, microstructure, and morphology of the nanocomposites were confirmed by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and field emission scanning electron microscopy (FE-SEM), and their water oxidation performance was examined in 0.1 M potassium hydroxide solution in the presence and absence of magnetic field. The results show that optimized GO/NiAl-LDH nanocomposite (GO-1 %/NiAl-LDH) exhibits the lowest overpotential compared with other prepared nanocomposites. This performance demonstrates comparable electroactivity to well-developed electrocatalysts like the perovskite-based electrodes, it also shows an improved electrocatalytic activity compared to NiAl-LDHs due to the presence of graphene oxide in the composite. We interpreted this significant performance to improve electron transform and high active site at the synthesized GO/NiAl-LDH composites. The best electrocatalytic activity with an overpotential of 443 and 473 mV at the current density 10 mA.cm−2 were evidenced for GO-1 %/NiAl-LDH nanocomposite in the presence and absence of external magnetic field, respectively. Furthermore, the tafel slope were reported about 54 and 162 mV.dec−1 in the presence and absence of magnetic field, respectively. This improved water oxidation can be attributed to the magneto-hydrodynamic effect and the increased number of metal sites on LDHs under the magnetic field.

Self-Etching Synthesis of Superhydrophilic Iron-Rich Defect Heterostructure-Integrated Catalyst with Fast Oxygen Evolution Kinetics for Large-Current Water Splitting.

Developing catalysts with rich metal defects, strong hydrophilicit, and extensive grain boundaries is crucial for enhancing the kinetics of electrocatalytic water oxidation and facilitating large-current water splitting. In this study, we utilized pH-controlled etching and gas-phase phosphating to synthesize a flower-like Ni2P-FeP4-Cu3P modified nickel foam heterostructure catalyst. This catalyst features pronounced hydrophilicity and a high concentration of Fe defects. It exhibits low overpotentials of 156 mV and 210 mV at current densities of 10 and 100 mA cm-2 respectively, and maintains stability for up to 200 h at 100 mA cm-2 with only 7.3% degradation, showcasing outstanding electrocatalytic water oxidation performance. Furthermore, when integrated into a Ni2P-FeP4-Cu3P/NF||Pt-C/NF electrolyzer, it achieves excellent overall water splitting performance, reaching current densities of 10 and 400 mA cm-2 at just 1.47 V and 1.73 V, respectively, and operates stably for 60 h at 500 mA cm-2 with minimal degradation. Analysis indicates that high-valence oxyhydroxides/phosphides of Ni, Fe, and Cu act as the primary active species. The presence of abundant Fe defects enhances electron transfer, strong hydrophilicity improves electrolyte contact, and numerous grain boundaries synergistically modulate the activation energy between active sites and oxygen-containing intermediates, significantly improving the kinetics of water oxidation.

The breakthrough of oxide pathway mechanism in stability and scaling relationship for water oxidation

Abstract An in-depth understanding of electrocatalytic mechanisms is essential for advancing electrocatalysts for the oxygen evolution reaction (OER). The emerging oxide pathway mechanism (OPM) streamlines direct O–O radical coupling, circumventing the formation of oxygen vacancy defects characteristic of the lattice oxygen mechanism (LOM) and bypassing additional reaction intermediates (*OOH) inherent to the adsorbate evolution mechanism (AEM). With only *O and *OH as intermediates, OPM-driven electrocatalysts stand out for their ability to disrupt traditional scaling relationships while ensuring stability. This review compiles the latest significant advances in OPM-based electrocatalysis, detailing design principles, synthetic methods, and sophisticated techniques to identify active sites and pathways. We conclude with prospective challenges and opportunities for OPM-driven electrocatalysts, aiming to advance the field into a new era by overcoming traditional constraints.

Carbonate-carbonate coupling on platinum surface promotes electrochemical water oxidation to hydrogen peroxide

Water electro-oxidation to form H2O2 is an important way to produce H2O2 which is widely applied in industry. However, its mechanism is under debate and HO(ads), hydroxyl group adsorbed onto the surface of the electrode, is regarded as an important intermediate. Herein, we study the mechanism of water oxidation to H2O2 at Pt electrode using in-situ Raman spectroscopy and differential electrochemical mass spectroscopy and find peroxide bond mainly originated from the coupling of two CO32- via a C2O62- intermediate. By quantifying the 18O isotope in the product, we find that 93% of H2O2 was formed via the CO32- coupling route and 7% of H2O2 is from OH(ads)-CO3•− route. The OH(ads)-OH(ads) coupling route has a negligible contribution. The comparison of various electrodes shows that the strong adsorption of CO3(ads) at the electrode surface is essential. Combining with a commercial cathode catalyst to produce H2O2 during oxygen reduction, we assemble a flow cell in which the cathode and anode simultaneously produce H2O2. It shows a Faradaic efficiency of 150% of H2O2 at 1 A cm−2 with a cell voltage of 2.3 V.

Elucidating the dynamics and transfer pathways of photogenerated charge carriers in V2O5/BiVO4 heterojunction photoanodes: A transient absorption spectroscopy study

Pairing of bismuth vanadate (BiVO4) with vanadium pentoxide (V2O5) forms a Type II heterojunction photoanode, which has been proven to be a high-performance photoanode architecture for efficient photoelectrochemical (PEC) water oxidation. To further support for advanced rational design and improvement of the heterojunction photoanode, it is quintessential to understand the mechanics and properties of photogenerated charge carriers formed. This study aims to probe the dynamics of photogenerated electron-hole pairs formed in pristine photoanode as well as the heterojunction photoanodes using transient absorption spectroscopy (TAS). Relative to the BiVO4/V2O5 structure, modelling and quantification of the decay constant helps in explaining why the V2O5/BiVO4 heterojunction photoanode exhibited a longer lifetime of the photogenerated charge carriers with a lower decay rate constant that leads to a much-improved overall generation of photocurrent density. An oxygen evolving catalyst of nickel oxyhydroxide (NiOOH) was then anchored on the exterior surfaces of the heterojunction photoanode system to further investigate and modify the transfer pathways of the photogenerated charge carriers. Furthermore, the hole- and scavenger-assisted TAS measurements on the BiVO4/V2O5 heterojunction photoanode revealed that the majority of trapped holes species are accumulated within the BiVO4 layer. The findings suggested that the Type II heterojunction formation in V2O5/BiVO4 could effectively reduce its charge recombination process.

High-Valence Metals Accelerate the Reaction Kinetics for Boosting Water Oxidation.

The transition metal with high valence state in oxyhydroxides can accelerate the reaction kinetics, enabling highly intrinsic OER activity. However, the formation of high-valence transition-metal ions is thermodynamically unfavorable in most cases. Here, a novel strategy is proposed to realize the purpose and reveal the mechanism by constructing amorphous phase and incorporating of elements with the characteristic of Lewis acid or variable charge state. A model catalyst, CeO2-NiFeOxHy, is presented to achieve the modulation of valence state of active site (Ni2+→Ni3+→Ni4+) for improved OER, leading to dominant active sites with high valence state. The CeO2-NiFeOxHy electrode exhibits superior OER performance with overpotential of 214 and 659mV at 10 and 500mAcm-2, respectively (without IR correction), and high stability, which are much better than those of NiOxHy, NiFeOxHy and CeO2-NiOxHy. These findings provide an effective strategy to achieve the active metals with high-valence state for highly efficient OER.

Anion‐Mediated Rapid and Direct Synthesis of FeNiOOH for Robust Water Oxidation

AbstractFeNiOOH is regarded as the most stable active species in the oxygen evolution reaction (OER), but the high oxidation energy of NiOOH poses a challenge to directly synthesize FeNiOOH as a real OER catalyst. Herein, an anion‐mediated kinetically controlled strategy is proposed, coupled with cation‐induced geometric topology modulation, to directly synthesis FeNiOOH with ultra‐thin, densely packed nanosheet architectures. Specifically, the Cl−‐mediated in situ generation of hypochlorous acid promotes the direct formation of NiFeOOH. Concurrently, high‐valence competitive Ru3+ mitigate electrostatic repulsion, fostering a compact and densely packed assembly of Ru/FeNiOOH nanosheet branches. Furthermore, the intrinsic electron‐capturing ability of FeOOH, in synergy with the stabilizing effect of doped Ru atoms, further promote the formation and stabilization high‐valence NiOOH. Consequently, the hierarchical Ru/FeNiOOH@NiPOx nanoarray catalyst displays exceptional OER performance, with an overpotential of 172 mV at 10 mA cm−2 and outstanding stability. This study provides a novel strategy to directly construct a real catalyst.

Unlocking the Electrocatalytic Behavior of Cu2MnS2 Nanoflake-Anchored rGO for the Oxygen Evolution Reaction in an Alkaline Medium.

A catalyst of the oxygen evolution reaction (OER) that is viable, affordable, and active for effective water-splitting applications is critical. A variety of electrocatalysts have been discovered to replace noble metal-based catalysts. Of these, transition metal-based sulfides are essential for incorporating carbonaceous materials to improve electrical conductivity, resulting in better electrocatalytic performance. Our study illustrates the synthesis of Cu2MnS2 (CMS) nanoflakes and their different rGO composites (10 to 40 wt %) via a hydrothermal technique for an effective water oxidation reaction. The X-ray diffraction pattern reveals that the prepared Cu2MnS2 nanoflakes exhibit a cubic crystal structure. The high-resolution scanning electron microscopy and the high resolution transmission electron microscopy images corroborate the formation of the nanoflake-like morphology of Cu2MnS2 with the strong interaction of rGO. The selected area electron diffraction analysis pattern reveals a polycrystalline nature. The Fourier transform infrared spectrum shows the existence of a metal sulfur vibrational band at 590 cm-1, and Raman analysis infers the presence of rGO. The X-ray photoelectron spectroscopy spectra reveal the oxidation states of the elements present in the samples. Using Brunauer-Emmett-Teller analysis, the surface area of CMS-20 is found to be 117.04 m2/g. The measured OER overpotentials using linear sweep volammetry and the values are 380, 370, 340, 376, and 400 mV at 10 mA/cm2 for CMS, CMS-10, CMS-20, CMS-30, and CMS-40, respectively, and the corresponding Tafel slope values are 179, 158, 149, 206, and 240 mV/decade, respectively. The electrochemical active surface area is estimated using cyclic voltammetry for all of the catalysts, where CMS-20 showed a larger surface area. Also, the same catalyst exhibits good stability for ∼24 h at a constant potential, which is confirmed via chronoamperometry. Thus, combining transition metal-based sulfides with carbonaceous materials indicates improved catalytic behavior for the preparation of high-performance OER electrocatalysts. Overall, the prepared CMS-20 performed as an efficient OER electrocatalyst and can be utilized for practical applications in energy conversion.

Al-etching-induced defect engineering in NiAl LDHs for promoting multifunctional electrocatalytic oxidations: Water oxidation and urea oxidation

Electrocatalytic water splitting is a promising avenue to produce green hydrogen for future sustainable development. Developing multifunctional catalysts with high-performance toward urea oxidation reaction (UOR) and oxygen evolution reaction (OER) offers a unique approach for simultaneously achieving the degradation of urea-containing wastewater and energy-saving hydrogen production. Ni-based materials are a kind of promising materials for electrocatalysis, since its abundant reserve and tolerance. However, low intrinsic activity and catalytic efficiency hinder its wide application. Here, a defect engineering strategy is developed to create vacancies on NiAl layer double hydroxides (LDHs) catalysts by selectively etching Al ions in strong alkaline solution. The obtained NiAl LDHs with rich defects (D-NiAl LDHs) exhibit good OER performance with overpotential of 264 mV to achieve a current density of 10 mA cm−2 and a Tafel slope of 39.8 mV dec−1. In addition, the D-NiAl LDHs catalysts also show excellent UOR activity using a potential of 1.328 V vs. RHE @ 10 mA cm−2 in alkaline solution. In comparation to NiAl LDHs, the enhanced performance of D-NiAl LDHs toward oxidation of small-molecule OH− and urea could be attributed to electronic regulation of defects and a larger electrochemical surface area. Partially replacing the OER with the UOR, the driving voltage of overall water splitting reduces effectively from 1.856 V to 1.688 V at a current of 100 mA cm−2.

Coupling multifunctional ZnCoAl-layered double hydroxides on Ti-Fe2O3 photoanode for efficient photoelectrochemical water oxidation

The efficiency of photoelectrochemical (PEC) water splitting is hindered by the slow kinetics of the oxygen evolution reaction (OER). This study developed a composite photoanode for water oxidation by incorporating ternary LDHs (ZnCoAl-LDH) onto Ti-Fe2O3 as a cocatalyst. The ZnCoAl-LDH/Ti–Fe2O3 photoanode achieved a photocurrent density of 3.51 mA/cm2 at 1.23 V vs. RHE, which is 9.8 times higher than that of bare Ti-Fe2O3. Through a series of characterizations, the synergistic effects among the three metals were revealed. Furthermore, the addition of Zn can induce the formation of more high-valent Co, increasing the conductivity of CoAl-LDH and significantly reducing the surface charge transfer resistance. These advantages significantly enhance the injection efficiency of ZnCoAl-LDH/Ti-Fe2O3 (82 %), thereby accelerating the OER kinetics of Ti-Fe2O3. Our work introduces new approaches for selecting photoelectrochemical cocatalysts and designing high-performance photoanodes for water splitting.

Strontium Doped IrOx Triggers Direct O-O Coupling to Boost Acid Water Oxidation Electrocatalysis.

The discovery of efficient and stable electrocatalysts for the oxygen evolution reaction (OER) in acidic conditions is crucial for the commercialization of proton-exchange membrane water electrolyzers. In this work, we propose a Sr(OH)2-assisted method to fabricate a (200) facet highly exposed strontium-doped IrOx catalyst to provide available adjacent iridium sites with lower Ir-O covalency. This design facilitates direct O-O coupling during the acidic water oxidation process, thereby circumventing the high energy barrier associated with the generation of *OOH intermediates. Benefiting from this advantage, the resulting Sr-IrOx catalyst exhibits an impressive overpotential of 207 mV at a current density of 10 mA cm-2 in 0.5 M H2SO4. Furthermore, a PEMWE device utilizing Sr-IrOx as the anodic catalyst demonstrates a cell voltage of 1.72 V at 1 A cm-2 and maintains excellent stability for over 500 hours. Our work not only provides guidance for the design of improved acidic OER catalysts but also encourages the development of iridium-based electrocatalysts with novel mechanisms for other electrocatalytic reactions.

Designing 1-nm-Thick MOF Nanosheets with Donor-Acceptor Complexes for Photosynthesis of H2O2 Using Water and Dioxygen Only.

Artificial photosynthesis of hydrogen peroxide (H2O2) presents a promising environmentally friendly alternative to the industrial anthraquinone process. This work designed ultrathin metal-organic framework (MOF) nanosheets on which porphyrin ligand as an electron donor (D) and anthraquinone (AQ) as an electron acceptor (A) are integrated as the D-A complexes. The porphyrin component allows the MOF nanosheets to absorb full-spectrum solar light while the acceptor AQ motif promotes central aluminum ion coordination, hindering layer stacking to achieve a thickness of 1.0 nm. The ultrathin D-A design facilitates the separation of electrons from the MOF skeleton to the AQ motif, which induces the direct two-electron oxygen reduction reaction (ORR) mediated by the reversible redox couple of AQ-AQH2 and multielectron water oxidation reaction (WOR) driven by holes remaining on the porphyrin part. In O2-saturated water, the ultrathin MOF nanosheets outperformed the AQ-free bulk and multilayered counterparts by 2.9 and 2.6 times in H2O2 production, respectively, achieving the apparent quantum yield of 4.8% at 420 nm. It also surpasses other benchmark photocatalysts, including the typical MOF photocatalyst, MIL-125-NH2, and organic polymeric photocatalysts. The ultrathin D-A MOF photocatalyst generated H2O2 via both two-electron ORR as a major path and two-electron WOR as a minor path. This approach presents a promising strategy for the rational design of efficient nanostructured photocatalysts for solar fuels and chemicals.

Oxidative reconstructed Ru-based nanoclusters forming heterostructures with lanthanide oxides for acidic water oxidation

Achieving rapid anodic oxygen evolution reaction (OER) kinetics and improving the stability of the corresponding ruthenium (Ru)-based catalysts is a current priority for the realisation of industrial water splitting. However, the activity and stability of O2 evolution in electrocatalysis are largely inhibited by the insufficient adsorption of the reactant H2O and too strong adsorption of the intermediate OOH*, as well as by the dissolution of the active site due to excessive oxidation. To solve this challenge, herein, we developed a regulatory strategy combining lanthanide oxides and metal oxidative reconfiguration. The introduction of Eu2O3 effectively promotes the adsorption of H2O, optimizes the adsorption energy of OOH*, and reduces the reaction energy barrier of acidic OER process. And the metal oxidation remodeling process exposed more active sites and prevented the peroxidation process. The optimized Ru/Eu2O3@CNT catalyst showed the highest catalytic activity and stability in acidic OER. Its mass activity was 1219.1 A gRu−1 and the TOF value reached 4.4 s−1 at 1.48 V. Additionally, Ru/Eu2O3@CNT after oxidative reconstruction demonstrates the industrially needed current density of 1.0 A cm−2 at 1.71 V in PEM electrolyser, achieving stability in excess of 200 h.