Water Oxidation Catalysts Research Articles

MXene-mediated reconfiguration induces robust nickel–iron catalysts for industrial-grade water oxidation

Nickel-iron oxy/hydroxides (NiFeOxHy) emerge as an attractive type of electrocatalysts for alkaline water oxidation reaction (WOR), but which encounter a huge challenge in stability, especially at industrial-grade large current density due to uncontrollable Fe leakage. Here, we tailor the Fe coordination by a MXene-mediated reconfiguration strategy for the resultant NiFeOxHy catalyst to alleviate Fe leakage and thus reinforce the WOR stability. The introduction of ultrafine MXene with surface dangling bonds in the electrochemical reconfiguration over Ni-Fe Prussian blue analogue induces the covalent hybridization of NiFeOxHy/MXene, which not only accelerates WOR kinetics but also improves Fe oxidation resistance against segregation. As a result, the NiFeOxHy coupled with MXene exhibits an extraordinary durability at ampere-level current density over 1,000 h for alkaline WOR with an ultralow overpotential of only 307 mV. This work provides a broad avenue and mechanistic insights for the development of nickel-iron catalysts toward industrial applications.

Ca-doped birnessite for enhanced photocatalysis of water oxidation

Birnessite is an affordable and high-efficiency catalyst for water oxidation. In this study, we attempted to doping Ca into birnessite to investigate the influence on its photocatalytic oxidation activity. The study was carried out through a combination of experimental investigations and DFT calculations of the relevant crystal and electronic structures. The analysis of Raman spectra using 2T2D correlation and DFT indicates that Ca contributes more to the high frequency regions (400–600 cm−1) than K. DFT further reveals that the introduction of Ca leads to an increase in the number of localized electrons at the Fermi energy level and in the conduction band. Photo-electrochemical experiments demonstrate a significant reduction of 100 mV/dec in the Tafel slope, along with a 1.48-fold increase in photo-current density for Ca-birnessite when compared to K-birnessite. In general, the results demonstrate that Ca-birnessite can effectively heighten visible light absorption, reduce the band gap, and enhance water oxidation activity.

An immobilized (carbene)nickel catalyst for water oxidation

The oxygen evolution reaction (OER) of water splitting is essential to electrochemical energy storage applications. While nickel electrodes are widely available heterogeneous OER catalysts, homogeneous nickel catalysts for OER are underexplored. Here we report two carbene-ligated nickel(II) complexes that are exceptionally robust and efficient homogeneous water oxidation catalysts. Remarkably, these novel nickel complexes can assemble a stable thin film onto a metal electrode through poly-imidazole bridges, making them supported heterogeneous electrochemical catalysts that are resilient to leaching and stripping. Unlike molecular catalysts and nanoparticle catalysts, such electrode-supported metal-complex catalysts for OER are rare and have the potential to inspire new designs. The electrochemical OER with our nickel-carbene catalysts exhibits excellent current densities with high efficiency, low Tafel slope, and useful longevity for a base metal catalyst. Our data show that imidazole carbene ligands stay bonded to the nickel(II) centers throughout the catalysis, which allows the facile oxygen evolution.

A Water-Stable Boronate Ester Cage.

The reversible condensation of catechols and boronic acids to boronate esters is a paradigm reaction in dynamic covalent chemistry. However, facile backward hydrolysis is detrimental for stability and has so far prevented applications for boronate-based materials. Here, we introduce cubic boronate ester cages 6 derived from hexahydroxy tribenzotriquinacenes and phenylene diboronic acids with ortho-t-butyl substituents. Due to steric shielding, dynamic exchange at the Lewis acidic boron sites is feasible only under acid or base catalysis but fully prevented at neutral conditions. For the first time, boronate ester cages 6 tolerate substantial amounts of water or alcohols both in solution and solid state. The unprecedented applicability of these materials under ambient and aqueous conditions is showcased by efficient encapsulation and on-demand release of β-carotene dyes and heterogeneous water oxidation catalysis after the encapsulation of ruthenium catalysts.

A halide perovskite based ternary heterojunction with multi-shell hollow structure for stable and efficient artificial photosynthesis

Low-cost halide perovskite materials hold great promise as photocatalysts for CO2 reduction. However, their inferior water-tolerance will lead to a substantial decline in activity during prolonged photocatalytic CO2 reduction with water as the electron source. Herein, we integrate a lead-free halide perovskite Cs3Bi2I9 as photoactive layer with TiO2 as water oxidation catalyst and g-C3N4 as CO2 reduction catalyst to construct a ternary heterojunction (TiO2/Cs3Bi2I9/g-C3N4) with a multi-shell hollow structure. The formation of heterojunction endows TiO2/Cs3Bi2I9/g-C3N4 composite with enhanced photocatalytic activity for CO2 reduction due to the improved photogenerated carrier separation. TiO2/Cs3Bi2I9/g-C3N4 achieves a CO yield of 120.6 μmol g−1 h−1 for photocatalytic CO2 reduction, which is 3.1 times higher than that of individual Cs3Bi2I9. More importantly, benefitting from the double-sided protection of g-C3N4 and TiO2, the photocatalytic CO2 reduction activity of TiO2/Cs3Bi2I9/g-C3N4 remains undiminished even over 100 h of continuous light irradiation, demonstrating significantly improved stability in water-contained reaction system.

First‐Row Transition‐Metal Complexes with Tetra‐Amido Macrocyclic Ligands for Water and C(sp3)−H Bond Oxidation: Performance Benchmarking Using Free Energy Relationships

AbstractThe catalytic oxidation of water and C(sp3)−H bonds enables the conversion of solar/electrochemical energy into chemical energy and alcohol fuel production, respectively, and therefore plays important roles in energy conversion/storage. These transformations are typically catalyzed by the highly active complexes of the earth‐abundant first‐row transition metals (Mn, Fe, Co, Ni, and Cu) with tetra‐amido macrocyclic ligands (TAMLs), although the related kinetics and thermodynamics remain underexplored. This review uses free energy relationships between kinetic and thermodynamic descriptors as normalized metrics to benchmark/compare these TAML‐based catalysts and assess the advances in their development.

Pivotal Role of Geometry Regulation on O-O Bond Formation Mechanism of Bimetallic Water Oxidation Catalysts.

In this study, we highlight the impact of catalyst geometry on the formation of O-O bonds in Cu2 and Fe2 catalysts. A series of Cu2 complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, the catalytic performance of these Cu2 complexes is enhanced as their molecular skeletons become more rigid, which contrasts with the behavior observed in our previous investigation with Fe2 analogs. Moreover, mechanistic studies reveal that the reactivity of the bridging O atom results in distinct pathways for O-O bond formation in Cu2 and Fe2 catalysts. In Cu2 systems, the coupling takes place between a terminal CuIII -OH and a bridging μ-O⋅ radical. Whereas in Fe2 systems, it involves the coupling of two terminal Fe-oxo entities. Furthermore, an in-depth structure-activity analysis uncovers the spatial geometric prerequisites for the coupling of the terminal OH with the bridging μ-O⋅ radical, ultimately leading to the O-O bond formation. Overall, this study emphasizes the critical role of precisely adjusting the spatial geometry of catalysts to align with the O-O bonding pathway.

Pivotal Role of Geometry Regulation on O−O Bond Formation Mechanism of Bimetallic Water Oxidation Catalysts

AbstractIn this study, we highlight the impact of catalyst geometry on the formation of O−O bonds in Cu2 and Fe2 catalysts. A series of Cu2 complexes with diverse linkers are designed as electrocatalysts for water oxidation. Interestingly, the catalytic performance of these Cu2 complexes is enhanced as their molecular skeletons become more rigid, which contrasts with the behavior observed in our previous investigation with Fe2 analogs. Moreover, mechanistic studies reveal that the reactivity of the bridging O atom results in distinct pathways for O−O bond formation in Cu2 and Fe2 catalysts. In Cu2 systems, the coupling takes place between a terminal CuIII−OH and a bridging μ−O⋅ radical. Whereas in Fe2 systems, it involves the coupling of two terminal Fe–oxo entities. Furthermore, an in‐depth structure–activity analysis uncovers the spatial geometric prerequisites for the coupling of the terminal OH with the bridging μ−O⋅ radical, ultimately leading to the O−O bond formation. Overall, this study emphasizes the critical role of precisely adjusting the spatial geometry of catalysts to align with the O−O bonding pathway.

Supramolecular Macrocycle Regulated Single‐Atom MoS2@Co Catalysts for Enhanced Oxygen Evolution Reaction

The development of active water oxidation catalysts for water splitting has stimulated considerable interest. Herein, the design and building of single atom Co sites using a supramolecular tailoring strategy are reported, that is, the introduction of pillar[4]arene[1]quinone (P4A1Q) permits mononuclear Co species stereoelectronically assembled on MoS2 matrix to construct an atomically dispersed MoS2@Co catalyst with modulated local electronic structure, definite chemical environment and enhanced oxygen evolution reaction performance. Theoretical calculations indicate that immsobilized single‐Co sites exhibit an optimized adsorption capability of oxygen‐containing intermediates, endowing the catalyst an excellent electrocatalytic oxygen evolution reaction activity, with a low overpotential of 370 mV at 10 mA cm−2 and a small Tafel slope of 90 mV dec−1. The extendable potential of this strategy to other electrocatalysts such as MoS2@Ni and MoS2@Zn, and other applications such as the hydrogen evolution reaction was also demonstrated. This study affords new insights into the rational design of single metal atom systems with enhanced electrocatalytic performance.

Thin-Film Composite Membranes for Hydrogen Evolution with a Saline Catholyte Water Feed.

Hydrogen gas evolution using an impure or saline water feed is a promising strategy to reduce overall energy consumption and investment costs for on-site, large-scale production using renewable energy sources. The chlorine evolution reaction is one of the biggest concerns in hydrogen evolution with impure water feeds. The "alkaline design criterion" in impure water electrolysis was examined here because water oxidation catalysts can exhibit a larger kinetic overpotential without interfering chlorine chemistry under alkaline conditions. Here, we demonstrated that relatively inexpensive thin-film composite (TFC) membranes, currently used for high-pressure reverse osmosis (RO) desalination applications, can have much higher rejection of Cl- (total crossover of 2.9 ± 0.9 mmol) than an anion-exchange membrane (AEM) (51.8 ± 2.3 mmol) with electrolytes of 0.5 M KOH for the anolyte and 0.5 M NaCl for the catholyte with a constant current (100 mA/cm2 for 20 h). The membrane resistances, which were similar for the TFC membrane and the AEM based on electrochemical impedance spectroscopy (EIS) and Ohm's law methods, could be further reduced by increasing the electrolyte concentration or removal of the structural polyester supporting layer (TFC-no PET). TFC membranes could enable pressurized gas production, as this membrane was demonstrated to be mechanically stable with no change in permeate flux at 35 bar. These results show that TFC membranes provide a novel pathway for producing green hydrogen with a saline water feed at elevated pressures compared to systems using AEMs or porous diaphragms.

Supramolecular interaction of a molecular catalyst with a polymeric carbon nitride photoanode enhances photoelectrochemical activity and stability at neutral pH.

Polymeric carbon nitride (CN) emerged as an alternative, metal-free photoanode material for water-splitting photoelectrochemical cells (PECs). However, the performance of CN photoanodes is limited due to the slow charge separation and water oxidation kinetics due to poor interaction with water oxidation catalysts (WOCs). Moreover, operation under benign, neutral pH conditions is rarely reported. Here, we design a porous CN photoanode connected to a highly active molecular Ru-based WOC, which also acts as an additional photo-absorber. We show that the strong interaction between the π-system of the heptazine units within the CN with the CH groups of the WOC's equatorial ligand enables a strong connection between them and an efficient electronic communication path. The optimized photoanode exhibits a photocurrent density of 180 ± 10 μA cm-2 at 1.23 V vs. the reversible hydrogen electrode (RHE) with 89% faradaic efficiency for oxygen evolution with turnover numbers (TONs) in the range of 3300 and a turnover frequency (TOF) of 0.4 s-1, low onset potential, extended incident photon to current conversion, and good stability up to 5 h. This study may lead to the integration of molecular catalysts and polymeric organic absorbers using supramolecular interactions.

Efficient electrochemical water oxidation catalyzed by N4-coordinated nickel complexes under neutral conditions

Two novel nickel complexes are reported for the first time. Both complexes can catalyze water oxidation under neutral conditions with low onset overpotential. Combined experiments confirm that they are genuine molecular water oxidation catalysts.

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.

Stabilization of Ni-containing Keggin-type polyoxometalates with variable oxidation states as novel catalysts for electrochemical water oxidation.

The development of new recyclable and inexpensive electrochemically active species for water oxidation catalysis is the most crucial step for future utilization of renewables. Particularly, transition metal complexes containing internal multiple, cooperative metal centers to couple with redox catalysts in the inorganic Keggin-type polyoxometalate (POM) framework at high potential or under extreme pH conditions would be promising candidates. However, most reported Ni-containing POMs have been highly unstable towards hydrolytic decomposition, which precludes them from application as water oxidation catalysts (WOCs). Here, we have prepared new tri-Ni-containing POMs with variable oxidation states by charge tailored synthetic strategies for the first time and developed them as recyclable POMs for water oxidation catalysts. In addition, by implanting corresponding POM anions into the positively charged MIL-101(Cr) metal-organic framework (MOF), the entrapped Ni2+/Ni3+ species can show complete recyclability for water oxidation catalysis without encountering uncontrolled hydrolysis of the POM framework. As a result, a low onset potential of approximately 1.46 V vs. NHE for water oxidation with stable WOC performance is recorded. Based on this study, rational design and stabilization of other POM-electrocatalysts containing different multiple transition metal centres could be made possible.

A ruthenium catalyst linked to a redox-active ruthenium polypyridine for water oxidation.

Chromophore-catalyst assemblies are interesting benchmark molecules for photocatalysis. We have prepared two examples of these assemblies and characterized their behaviour as catalysts for the water oxidation reaction. In the bimetallic complexes [Ru(tpy)(4,4'-X2-bpy)(μ-CN)Ru(bda)(DMSO)](PF6) (X = -H (1), -OCH3 (2), tpy = 2,2':6',2''-terpyridine, bpy = 2,2'-bipyridine, H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid and DMSO = (CH3)2SO), a Ru(II)-polypiridine chromophore {Ru(tpy)(4,4'-X2-bpy)} is linked by a cyanide bridge to a {Ru(bda)} water oxidation catalyst. Both complexes catalyze water oxidation both chemically, using Ce(IV) as the terminal oxidant, and electrochemically. Electrochemical and spectroelectrochemical studies, aided with (TD)DFT calculations, allowed us to study the different species involved in the catalytic cycle. For the RuIIRuIII, an intense MMCT (metal-to-metal charge transfer) band suggests a geometrical reorganization during the oxidation process. The wave associated with oxidation to the RuIIIRuIV species shows an increased current that suggests that it may be a catalyst for the water oxidation reaction. Further oxidation results in the RuIIIRuV redox state which is an active catalyst for the water oxidation reaction as demonstrated by the evolution of oxygen.

An artificial metalloenzyme that can oxidize water photocatalytically: design, synthesis, and characterization

A protein-based catalyst for photoactivated water oxidation was successfully constructed from CoSalen bound to cytochrome b5. The protein scaffold prevents the formation of large CoOx nanoparticles and strongly improves catalyst solubility.

Distribution of high valence Fe sites in nickel–iron hydroxide catalysts for water oxidation

Nickel–iron (Ni–Fe) hydroxides have received much attention as abundant and efficient electrocatalysts for the oxygen evolution reaction (OER) under alkaline conditions.

Thermally activated growth of ternary oxyhydroxides on perovskites for efficient water oxidation.

Perovskite oxides are promising catalysts for water oxidation. Herein, we constructed a Sr3CoFeWO9 triple perovskite with Co, Fe, and W atoms sharing octahedral positions. Thermally activated growth of an amorphous FeCoW oxyhydroxide layer on this perovskite pre-catalyst greatly enhanced the oxygen evolution reaction (OER) activities, reducing overpotential at 10 mA cm-2geo by 115 mV. This highlights the benefits of compositional design and structural reconstruction for efficient electrocatalytic materials.

Integration of surface polymerization and self-assembly strategies for heterogenization of copper-based catalysts for water oxidation

Integration of surface polymerization and self-assembly strategies for heterogenization of copper-based catalyst leads to sustainable high efficiency for water oxidation.

Spin configuration modulation of Co3O4 by Ru doping for boosting the overall water splitting and hydrazine oxidation reactions

Co-based spinel oxides with unique crystal structures have been identified as a class of promising candidates for alkaline water oxidation catalysis in oxide structural families.