Benchmark IrO2 Research Articles

Iridium Single-Atom-Ensembles Stabilized on Mn-Substituted Spinel Oxide for Durable Acidic Water Electrolysis.

Exploring single-atom-catalysts for the acidic oxygen evolution reaction (OER) is of paramount importance for cost-effective hydrogen production via acidic water electrolyzers. However, the limited durability of most single-atom-catalysts and Ir/Ru-based oxides under harsh acidic OER conditions, primarily attributed to excessive lattice oxygen participation resulting in metal-leaching and structural collapse, hinders their practical application. Herein, an innovative strategy is developed to fabricate short-range Ir single-atom-ensembles (IrSAE) stabilized on the surface of Mn-substituted spinel Co3O4 (IrSAE-CMO), which exhibits excellent mass activity and significantly improved durability (degradation-rate: ≈2mVh-1), outperforming benchmark IrO2 (≈44mVh-1) and conventional Irsingle-atoms on pristine-Co3O4 for acidic OER. First-principle calculations reveal that Mn-substitution in the octahedral sites of Co3O4 substantially reduces the migration energy barrier for Irsingle-atoms on the CMO surface compared to pristine-Co3O4, facilitating the migration of Irsingle-atoms to form strongly correlated IrSAE during pyrolysis. Extensive ex situ characterization, operando X-ray absorption and Raman spectroscopies, pH-dependence activity tests, and theoretical calculations indicate that the rigid IrSAE with appropriate Ir-Ir distance stabilized on the CMO surface effectively suppresses lattice oxygen participation while promoting direct O─O radical coupling, thereby mitigating Ir-dissolution and structural collapse, boosting the stability in an acidic environment.

Controlled formation of CoOOH/Co(III)-MOF active phase for boosting electrocatalytic alkaline water oxidation

Surface reconstituted metal-organic frameworks (MOFs) offer appealing properties for electrocatalysis due to their unique structural and compositional advantages. In this work, a controlled potential-induced reconstruction of a two-dimensional cobalt metal-organic framework for boosting oxygen evolution reaction in alkaline media is reported. The current MOF is shown to undergo a partial structural transformation that generates a heterogeneous system, where the original MOF coexists with an oxyhydroxide phase. In fact, the potential-induced stabilization of Co(III) metal centers in the MOF is crucial for delaying its full degradation in alkaline media. This partial retention of the Co(III)MOF phase in the so-derived heterogeneous catalyst has been demonstrated to be decisive for boosting the alkaline electrocatalytic oxygen evolution reaction (OER), displaying superior OER activity in terms of both thermodynamic and kinetic merits compared to the benchmark IrO2 and RuO2 electrocatalysts and the prototypical cobalt (oxy)hydroxides, with a Tafel slope of 52 mV dec−1 and a turnover frequency (TOF) of 6.8 s−1 at 450 mV. Remarkably, the generated final product is stable, exhibiting high robustness and long durability for long-term OER electrolysis. This work provides new insight into the impact of the reconstruction of a MOF for alkaline OER under typical electrochemical conditions, which ultimately benefits the rational design of MOF-based catalysts with high electrocatalytic activity for oxidation reactions.

Electrochemically Created Active Centers in a Bimetallic CoNi-Triazole Metal-Organic Framework for Enhanced Oxygen Evolution Reaction Activity.

Electrochemical water oxidation utilizing bimetallic CoNi-Tz (Tz = 1,2,4-triazole) framework is explored. Initially, CoNi-Tz possesses active tetrahedral Co center and electron-mediated octahedral Ni chain. After performing an electrochemical activation, the partial structural transformation on the Ni center occurs. This leads to the generation of excessive active centers which can promote catalytic activity of the framework. The activated CoNi-Tz catalyst displays a remarkably low OER overpotential of 293 mV at a current density of 10 mA cm-2 with a small Tafel slope of 49.98 mV dec-1, outperforming the single metal Co-Tz and benchmark IrO2 catalysts.

Understanding the Role of Strain on Electrochemical Reaction Kinetics: Oxygen Evolution on Mechanically Strained Rutile TiO2 As a Model System

Electrocatalysis offers a green alternative (when coupled with renewably-sourced electrons) to conventional carbon-intensive chemical fuel and commodity production processes. Electrochemical device efficiency, however, is limited by the sluggish kinetics of multi-electron transfer reactions, such as the oxygen evolution reaction (OER). Theoretical adsorption free energy scaling relationships predict large oxygen evolution overpotentials (>370 mV) for metal oxides performing the adsorbate evolution mechanism, a series of four proton-concerted electron transfer steps.1 Identifying catalyst design strategies that overcome or “break” scaling relations (i.e. strain,2 high entropy alloys,3 non-concerted proton and electron transfer mechanisms4,5) would provide a means to lower kinetic potential energy penalties and enhance the efficiency and economic incentives for further development of renewably-driven electrochemical reactions.Here we investigate the role of mechanically induced strain on the OER activity of polycrystalline rutile TiO2 thin films, grown on the super elastic alloy nitinol (NiTi) and mechanically strained by tensile tester. Our work characterizes how strain manifests in these complex polycrystalline systems with complementary physical characterization techniques (e.g. X-ray diffraction and Raman spectroscopy) and relates strain to OER performance in alkaline electrolytes. We contextualize our results within the framework of conventional adsorption scaling relationships to hypothesize how tensile strain influences reaction intermediate adsorption affinities, inferring implications for the OER kinetics of benchmark IrO2 and RuO2 catalysts that share the same crystal structure as the rutile TiO2 considered here.(1) Jaramillo, T. F.; Nørskov, J. K.; Rossmeisl, J. Universality in Oxygen Evolution Electrocatalysis on Oxide Surfaces. ChemCatChem 2011, 3 (7), 1159–1165. https://doi.org/10.1002/cctc.201000397.(2) Khorshidi, A.; Violet, J.; Hashemi, J.; Peterson, A. A. How Strain Can Break the Scaling Relations of Catalysis. Nat Catal 2018, 1 (4), 263–268. https://doi.org/10.1038/s41929-018-0054-0.(3) Kante, M. V.; Weber, M. L.; Ni, S.; van den Bosch, I. C. G.; van der Minne, E.; Heymann, L.; Falling, L. J.; Gauquelin, N.; Tsvetanova, M.; Cunha, D. M.; Koster, G.; Gunkel, F.; Nemšák, S.; Hahn, H.; Velasco Estrada, L.; Baeumer, C. A High-Entropy Oxide as High-Activity Electrocatalyst for Water Oxidation. ACS Nano 2023, 17 (6), 5329–5339. https://doi.org/10.1021/acsnano.2c08096.(4) Grimaud, A.; Diaz-Morales, O.; Han, B.; Hong, W. T.; Lee, Y.-L.; Giordano, L.; Stoerzinger, K. A.; Koper, M. T. M.; Shao-Horn, Y. Activating Lattice Oxygen Redox Reactions in Metal Oxides to Catalyse Oxygen Evolution. Nature Chem 2017, 9 (5), 457–465. https://doi.org/10.1038/nchem.2695.(5) Yoo, J. S.; Rong, X.; Liu, Y.; Kolpak, A. M. Role of Lattice Oxygen Participation in Understanding Trends in the Oxygen Evolution Reaction on Perovskites. ACS Catal. 2018, 8 (5), 4628–4636. https://doi.org/10.1021/acscatal.8b00612.

High performance oxygen reduction and evolution reactions by graphitization of nickel –cobalt framework system

This study presents the successful synthesis of metal-organic frameworks (MOFs) via a simple one-pot method, followed by pyrolysis at 1000 °C to be used in the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). A study utilizing various techniques, including field emission scanning electron microscopy (FESEM), energy-dispersive X-ray spectroscopy (EDS), transmission electron microscopy (TEM), and X-ray diffraction (XRD), investigated the properties of NiCo-MOF and its individual components before and after pyrolysis.The pristine MOFs exhibited limited electrochemical stability for both ORR and OER, while the pyrolyzed MOFs demonstrated a significant enhancement and excellent long-term stability in OER and ORR performance in alkaline media. Notably, the OER performance rivaled that of the benchmark IrO2 electrocatalyst, with similar onset potentials (1.48 V for IrO2, 1.52 V, 1.56 V, and 1.59 V for pyrolyzed NiCo-MOF, Co-MOF, and Ni-MOF, respectively). Furthermore, the pyrolyzed MOF catalysts displayed promising ORR activity in a 0.1 M KOH solution under O2 saturation, as evidenced by their onset potentials (around 0.615 V, 0.63 V, and 0.7 V vs. RHE) and favorable Tafel slopes (53, 84, and 154 mV dec⁻1, for graphitizated Ni-MOF, Co-MOF, and NiCo-MOF, respectively). These findings demonstrate the effectiveness of pyrolysis in engineering the MOF crystal structure for enhanced catalytic performance. This paves the way for further exploration of this synthesis method for the design of structurally optimized catalysts and applicable to a broad spectrum of energy technologies.

Facet-Dependent Surface Restructuring on Nickel (Oxy)hydroxides: A Self-Activation Process for Enhanced Oxygen Evolution Reaction.

Unraveling the catalyst surface structure and behavior during reactions is essential for both mechanistic understanding and performance optimization. Here we report a phenomenon of facet-dependent surface restructuring intrinsic to β-Ni(OH)2 catalysts during oxygen evolution reaction (OER), discovered by the correlative ex situ and operando characterization. The ex situ study after OER reveals β-Ni(OH)2 restructuring at the edge facets to form nanoporous Ni1-xO, which is Ni deficient containing Ni3+ species. Operando liquid transmission electron microscopy (TEM) and Raman spectroscopy further identify the active role of the intermediate β-NiOOH phase in both the OER catalysis and Ni1-xO formation, pinpointing the complete surface restructuring pathway. Such surface restructuring is shown to effectively increase the exposed active sites, accelerate Ni oxidation kinetics, and optimize *OH intermediate bonding energy toward fast OER kinetics, which leads to an extraordinary activity enhancement of ∼16-fold. Facilitated by such a self-activation process, the specially prepared β-Ni(OH)2 with larger edge facets exhibits a 470-fold current enhancement than that of the benchmark IrO2, demonstrating a promising way to optimize metal-(oxy)hydroxide-based catalysts.

Stepwise Understanding on Hydrolysis Formation of the IrOx Nanoparticles as Highly Active Electrocatalyst for Oxygen Evolution Reaction

In this study, we have investigated the synthesis of supported iridium oxide (IrOx) nanoparticles (NPs) through hydrolysis in a surfactant-free aqueous bath as a possible route for the large-scale production of highly active electrocatalyst for oxygen evolution reaction (OER) in acidic water electrolyzers. The process involves (i) formation of Ir-hydroxides complex from an Ir precursor in basic media followed by (ii) protonation in acidic media to form colloidal hydrated IrOx NPs and (iii) conversion and deposition of IrOx NPs on the surface of carbon or TiN support by probe sonication. The IrOx NPs produced through hydrolysis route form highly stable colloidal solution. Since it is essential to precipitate the catalyst NPs from the colloidal solution for their use in water electrolyzer electrode development, here, we investigate the optimal reaction conditions, e.g., pH, temperature, time, and presence of support, for efficient synthesis of the catalyst NPs. The reaction intermediates formed at different reaction steps are explored to get insights into the chemistry of the process. Under the optimal synthesis conditions, 100% precipitation of IrOx NPs was achieved. Further, the precipitated TiN supported IrOx NPs exhibited high OER activity, superior to that of the commercial benchmark IrO2 electrocatalyst. The study provides a scalable synthesis route for highly active, low Ir-content OER electrocatalysts for acidic water electrolyzers. Graphical

Constructing quasi‐amorphous cobalt oxyhydroxide nanowires with synergy of anion and cation via ion exchange reconstruction for large-current–density oxygen generation

Deep insight into the synergy between anion and cation aids in the maximization of catalytic activity and the rational exploitation of efficient oxygen-evolving catalysts. However, how to use ion exchange reconstruction to devise highly active and cost-efficient oxygen evolution reaction (OER) catalysts with anion and cation synergies for water electrolysis is rarely reported. Herein, the cobalt triphosphide (CoP3) nanowires are elaborately devised as a component-flexible precatalyst for directing an anodic reconfiguration with Ni cation exchange to construct a highly active and quasi‐amorphous cobalt oxyhydroxide (CoOOH) catalyst integrated with cation (Ni) substitution and oxyanion (PO43-) decoration (denoted by R-(Ni)CoP3). Interestingly, the structural evolution and the Ni cation exchange processes are captured through various in/ex situ techniques. The resultant R-(Ni)CoP3 nanowires display a splendid activity with low overpotentials of 406 and 420 mV to respectively deliver industrial grade current densities of 1000 and 1500 mA cm−2, and an outstanding stability over 300 h at a large current density of 500 mA cm−2, superior to most progressive cobalt-based OER materials and the benchmark IrO2. The combination of theoretical calculations with experimental studies demonstrate that the synergy of cation (Ni) substitution and oxyanion (PO43-) decoration can significantly modulate the electronic states of CoOOH and optimize the adsorption free energy of OER intermediates, thus immensely expediting the kinetics process and enhancing the charge transfer ability and the intrinsic OER activity. This research suggests ion-regulatory reconfiguration as a flexible and changeable strategy to construct various efficient and advanced catalysts for water electrolysis and beyond.

Engineering Metallic Alloy Electrode for Robust and Active Water Electrocatalysis with Large Current Density Exceeding 2000mAcm-2.

The amelioration of brilliantly effective electrocatalysts working at high current density for the oxygen evolution reaction (OER) is imperative for cost-efficient electrochemical hydrogen production. Yet, the kinetically sluggish and unstable catalysts remain elusive to large-scale hydrogen (H2) generation for industrial applications. Herein, a new strategy is demonstrated to significantly enhance the intrinsic activity of Ni1-xFex nanochain arrays through a trace proportion of heteroatom phosphorus doping that permits robust water splitting at an extremely large current density of 1000 and 2000mAcm-2 for 760h. The in situ formation of Ni2P and Ni5P4 on Ni1-xFex nanochain arrays surface and hierarchical geometry of the electrode significantly promote the reaction kinetics and OER activity. The OER electrode provides exceptionally low overpotentials of 222 and 327mV at current densities of 10 and 2000mAcm-2 in alkaline media, dramatically lower than benchmark IrO2 and is among the most active catalysts yet reported. Remarkably, the alkaline electrolyzer renders a low voltage of 1.75V at a large current density of 1000mAcm-2, indicating outperformed overall water splitting. The electrochemical fingerprints demonstrate vital progress toward large-scale H2 production for industrial water electrolysis.

High-Entropy Carbonates (Ni-Mn-Co-Zn-Cr-Fe) as a Promising Electrocatalyst for Alkalized Seawater Oxidation

Direct seawater splitting has attracted considerable attention as an alternative to conventional alkaline water electrolysis because the former avoids the use of limited freshwater resources. However, several challenges must be overcome to realize direct seawater electrolysis. Most importantly, electrocatalysts for the anodic oxygen evolution reaction (OER) should exhibit high activity, stability, and selectivity in highly corrosive environments with abundant chloride ions. In this study, we developed high-entropy carbonate (HEC) as a promising electrocatalyst for seawater oxidation. In HECs, physicochemical interactions among different elements can effectively suppress the corrosion of OER active sites, while polyanionic CO32- can act as a corrosion-protective species by repelling negatively charged chloride ions during electrolysis. Consequently, HECs demonstrate outstanding catalytic activity, stability, and selectivity for seawater oxidation, surpassing those of ternary, quaternary, and quinary carbonates and even benchmark IrO2 catalysts.

Phase Electronic Structure Tuning via Pt, P-Doped Ni4Mo-Implanted Ti4O7 for Highly Efficient Water Splitting and Mg/Seawater Batteries.

Fine-tuning nanoscale structures, morphologies, and electronic states are crucial for creating efficient water-splitting electrocatalysts. In this study, a method for electronic structure engineering to enhance overall water splitting in a corrosion-resistant electrocatalyst matrix by integrating Pt, P dual-doped Ni4Mo electrocatalysts onto a Ti4O7 nanorod grown on carbon cloth (Pt, P-Ni4Mo-Ti4O7/CC) is introduced. By optimizing platinum and phosphorus concentrations to 1.18% and 2.42%, respectively, low overpotentials are achieved remarkably: 24mV at 10mA cm-2 for the hydrogen evolution reaction and 290mV at 20mA cm-2 for the oxygen evolution reaction in 1.0m KOH. These values approach or surpass those of benchmark Pt-C and IrO2 catalysts. Additionally, the Pt, P-Ni4Mo-Ti4O7/CC bifunctional electrocatalyst displays low cell potentials across various mediums, maintaining excellent current retention (96% stability after 40 h in mimic seawater at 20mA cm-2) and demonstrating strong corrosion resistance and suitability for seawater electrolysis. As a cathode in magnesium/seawater batteries, it achieves a power density of 7.2mW cm-2 and maintains stability for 100 h. Density functional theory simulations confirm that P, Pt doping-assisted electronic structure modifications augment electrical conductivity and active sites in the hybrid electrocatalysts.

Dinitrosyl Iron Complex-Derived Nanosized Zerovalent Iron (NZVI) as a Template for the Fe-Co Cracked NZVI: An Electrocatalyst for the Oxygen Evolution Reaction.

Nanosized zerovalent iron (NZVI) Fe@Fe3O4 with a core-shell structure derived from photocatalytic MeOH aqueous solution of dinitrosyl iron complex (DNIC) [(N3MDA)Fe(NO)2] (N3MDA = N,N-dimethyl-2-(((1-methyl-1H-imidazole-2-yl)methylene)amino)ethane-1-amine) (1-N3MDA), eosin Y, and triethylamine (TEA) is demonstrated. The NZVI Fe@Fe3O4 core shows a high percentage of zerovalent iron (Fe0 %) and is stabilized by a hydrophobic organic support formed through the photodegradation of eosin Y hybridized with the N3MDA ligand. In addition to its well-known reductive properties in wastewater treatment and groundwater remediation, NZVI demonstrates the ability to form heterostructures when it interacts with metal ions. In this research, Co2+ is employed as a model contaminant and reacted with NZVI Fe@Fe3O4 to result in the formation of a distinct Fe-Co heterostructure, cracked NZVI (CNZVI). The slight difference in the standard redox potentials between Fe2+ and Co2+, the magnetic properties of Co2+, and the absence of surface hydroxides of Fe@Fe3O4 enable NZVI to mildly reduce Co2+ and facilitate Co2+ penetration into the iron core. Taking advantage of the well-dispersed nature of CNZVI on an organic support, the reduction in particle size due to Co2+ penetration, and Fe-Co synergism, CNZVI is employed as a catalyst in the alkaline oxygen evolution reaction (OER). Remarkably, CNZVI exhibits a highly efficient OER performance, surpassing the benchmark IrO2 catalyst. These findings show the potential of using NZVI as a template for synthesizing highly efficient OER catalysts. Moreover, the study demonstrates the possibility of repurposing waste materials from water treatment as valuable resources for catalytic energy conversion, particularly in water oxidation processes.

TiNxOy/TiN Supported Ir-Oxide/Ir As Efficient OER Electrocatalyst for Acidic Water Electrolysis

Increasing the mass activity of Iridium-based electrocatalysts for oxygen evolution reaction (OER) is of significant importance for sustainable acidic water electrolyzers generating green hydrogen. Here, we have studied surface oxidized TiN (TiNxOy/TiN) as a catalyst support for Ir-based OER electrocatalysts with high mass activity. TiNxOy/TiN supported Ir-oxide/Ir nanoparticles were synthesized using a microwave-assisted approach. The synthesized IrO2@Ir/TiN with an Ir loading of 40 wt% exhibits a mass-normalized OER activity of ~2.4 times that of a commercial benchmark IrO2 OER electrocatalyst. The synthesized TiNxOy/TiN supported Ir-oxide/Ir catalyst, owing to superior utilization of the active catalyst surface and improved intrinsic activity through catalyst-support interaction, enables significant (~60 wt.%) reduction in the Ir metal loading required to obtain equivalent OER performance, compared to commercial benchmark. In addition, accelerated stress test (AST) involving potential cycling in acidic media suggest the IrO2@Ir/TiN catalyst to be of relatively higher durability (activity retention: 79%) compared to that of the commercial equivalent (activity retention: 66%). In the presentation, we discuss the findings focusing on impacts of surface chemistry of the synthesized catalysts on their mass-activity and the degradation mechanisms during AST. The study opens a new perspective for further research towards development of low-Ir loading OER electrocatalysts. Reference Karade, S. S.; Sharma, R.; Gyergyek, S.; Morgen, P.; Andersen, S. M., ChemCatChem 2023, e202201470, DOI: https://doi.org/10.1002/cctc.202201470.

Tuning graphitic carbon nitride (g-C3N4) electrocatalysts for efficient oxygen evolution reaction (OER)

Nowadays, energy conversion and storage technologies are essential research topics due to the necessity of more sustainable processes. Specifically, water splitting is highly affected by slow kinetics and limited knowledge of the oxygen evolution reaction (OER). This work envisages the preparation of graphitic carbon nitride (g-C3N4) electrocatalysts for efficient OER by a facile one-pot method. The impact of the preparation temperature (450–650 °C) of g-C3N4 was assessed for the first time on water splitting processes and explained by different characterisation techniques. The unique crystal structure, surface chemistry, and electronic properties of the material prepared at 550 °C lead to a remarkable OER efficiency, with an overpotential of 355 mV at 10 mA cm−2 and a Tafel slope of 46.8 mVdec−1. Interestingly, three major differences were observed when comparing the material prepared at 550 °C with those obtained at other temperatures: the reduced structural distortion, the superior composition in oxygen and the presence of terminal functional groups. Also, compared to other metal-free g-C3N4 electrocatalysts reported in the literature, we achieved lower Tafel slope values without additional post-treatments or co-catalysts. Hence, for the first time a metal-free catalyst defeats benchmark IrO2. The prepared electrodes were stable for up to 45 h, even when increasing the applied current density to 100 mA cm−2 for 15 h. Thus, this work provides a simple route for the fabrication of highly-efficient and long-lasting electrocatalysts for a remarkable OER performance.

On the Effect of the Nature of Carbon Nanostructures on the Activity of Bifunctional Catalysts Based on Manganese Oxide Nanowires

Manganese oxide nanowires (MONW) combined with carbon nanostructures were synthesized using three different carbon materials, and their effect on the activity towards Oxygen Reduction Reaction (ORR) and Oxygen Evolution Reaction (OER) was investigated in alkaline electrolytes. The carbon structures were carbon nanofibers (CNF), multiwall carbon nanotubes (CNT) and reduced graphene oxide (rGO). Both MONW and carbon nanostructures were characterized by X-ray diffraction, scanning and transmission electron microscopy, N2 physisorption and X-ray photoelectron spectroscopy. The electrochemical activity was assessed in a three-electrode cell. Composite MONW/CNF showed the best activity towards ORR, and MONW/rGO exhibited the highest activity towards OER of the series. The addition of the carbon nanostructures to MONW increased the number of electrons transferred in the ORR, indicating a synergistic effect between the carbon and manganese oxide structures due to changes in the reaction pathway. The analysis of Tafel slopes and electrochemical impedance spectroscopies showed that carbons and MONW catalyze different steps of the reactions, which explains the better activity of the composites. This led us to synthesize a MONW/rGO-CNF composite, where rGO-CNF is a hybrid carbon material. Composite MONW/rGO-CNF showed an improved activity towards ORR, close to the benchmark Pt/C catalyst, and activity towards OER, close to MONW/rGO, and better than the benchmark IrO2 catalyst. It also showed remarkable stability in challenging operation conditions.

Amorphous-Crystalline Interfaces on Hollow Nanocubes Derived from Ir-Doped Ni-Fe-Zn Prussian Blue Analog Enables High Capability of Alkaline/Acidic/Saline Water Oxidations.

Development of highly efficient and robust electrocatalysts for oxygen evolution reaction (OER) under specific electrolyte is a key to actualize commercial low-temperature water electrolyzers. Herein, a rational catalyst design strategy is first reported based on amorphous-crystalline (a-c) interfacial engineering to achieve high catalytic activity and durability under diverse electrolytes that can be used for all types of low-temperature water electrolysis. Abundant a-c interface (ACI) is implemented into a hollow nanocubic (pre)-electrocatalyst which is derived from Ir-doped Ni-Fe-Zn Prussian blue analogues (PBA). The implemented c-a interface is well maintained during prolonged OER in alkaline, alkalized saline, and acidic electrolytes demonstrating its diverse functionality for water electrolysis. Notably, the final catalyst exhibits superior catalytic activity with excellent durability for OER compared to that of benchmark IrO2 catalyst, regardless of chemical environment of electrolytes. Hence, this work can be an instructive guidance for developing the ACI engineered electroctalyst which can be diversely used for different types of low-temperature electrolyzers.

Coupling ferromagnetic ordering electron transfer channels and surface reconstructed active species for spintronic electrocatalysis of water oxidation

Sluggish reaction kinetics of oxygen evolution reaction (OER), resulting from multistep proton-coupled electron transfer and spin constriction, limits overall efficiency for most reported catalysts. Herein, using modeled ZnFe2−xNixO4 (0 ≤ x ≤ 0.4) spinel oxides, we aim to develop better OER electrocatalyst through combining the construction of ferromagnetic (FM) ordering channels and generation of highly active reconstructed species. The number of symmetry-breaking Fe–O–Ni structure links to the formation of FM ordering electron transfer channels. Meanwhile, as the number of Ni3+ increases, more ligand holes are formed, beneficial for redirecting surface reconstruction. The electro-activated ZnFe1.6Ni0.4O4 shows the highest specific activity, which is 13 and 2.5 times higher than that of ZnFe2O4 and unactivated ZnFe1.6Ni0.4O4, and even superior to the benchmark IrO2 under the overpotential of 350 mV. Applying external magnetic field can make electron spin more aligned, and the activity can be further improved to 39 times of ZnFe2O4. We propose that intriguing FM exchange-field interaction at FM/paramagnetic interfaces can penetrate FM ordering channels into reconstructed oxyhydroxide layers, thereby activating oxyhydroxide layers as spin-filter to accelerate spin-selective electron transfer. This work provides a new guideline to develop highly efficient spintronic catalysts for water oxidation and other spin-forbidden reactions.

Polymeric cobalt phthalocyanine on nickel foam as an efficient electrocatalyst for oxygen evolution reaction

Renewable energy is of prime importance for sustainable development. Hydrogen is considered as clean as well as an efficient energy source. In addition to H2 as fuel, polymer electrolyte membrane fuel cell requires oxygen as an oxidant. Electrocatalytic or photocatalytic water splitting processes yield H2 and O2. Compared to hydrogen evolution reaction (HER), the oxygen evolution reaction (OER) in water electrolysis is a very sluggish and slow process. Even precious and costly catalysts have demonstrated higher overpotential for OER. To overcome the issues related to overpotential as well as cost and durability, bio-inspired macrocycles and polymers based on phthalocyanine are being explored extensively because of their unique and versatile properties. In this effort, a novel cobalt phthalocyanine polymer (poly-CoTPzPyCPc) was synthesised and employed as a low-cost and efficient organic-based catalyst for OER. The characterized polymeric catalyst was coated on Ni foam and the fabricated electrodes were evaluated for OER in 0.1 M KOH. The electrodes Ni-foam, Ni/poly-CoTPzPyCPc, Ni/IrO2, and Ni/poly-CoTPzPyCPc + IrO2 exhibited an onset potential for OER at 1.57, 1.53, 1.47 and 1.43 V Vs. RHE, respectively. The Ni/poly-CoTPzPyCPc exhibited an overpotential of 365 mV (±2 mV) at a current density of 10 mA cm−2. Furthermore, the composite of poly-CoTPzPyCPc with IrO2, displayed surprisingly superior OER activity. The composite achieved a current density of 10 mA cm−2 at lower overpotential of 274 mV (±2 mV) than the polymeric phthalocyanine and benchmark IrO2 catalyst which showed an overpotential of 324 mV at the same current density. The Tafel slope value was found to be 89, 67, 34 and 31 mV/dec for pure Ni foam, Ni/poly-CoTPzPyCPc, Ni/IrO2 and Ni/poly-CoTPzPyCPc + IrO2, respectively. The stability studies performed on poly-CoTPzPyCPc + IrO2 composite catalyst revealed that the proposed catalyst is stable and can be successfully employed for OER in water electrolysis. The developed composite catalyst has a small amount loading of precious catalyst with simple organic based catalyst to achieve efficiency better than benchmark catalyst for OER.

In situ generation of FeOOH/NiOOH interface in FeS2/NiS2 nanosheets through deep reconstruction for efficient oxygen evolution reaction

Transition metal sulfides (TMSs) for electrochemical water splitting undergo significant self-reconstruction to form actual active species favorable for high oxygen evolution reaction (OER) performance. However, the complete self-reconstruction of most reported TMSs in alkaline media is unfrequent and the active species cannot be efficiently used. Herein, self-supported FeS2/NiS2 nanosheet arrays (FeNiS) are deliberately fabricated as pre-catalysts and then accomplished deep phase transformation into low-crystalline and ultrathin FeOOH/NiOOH (FeNiS-R) nanosheets favorable to alkaline OER. Various ex situ characterization studies uncover that the FeNiS-R with abundant interfaces is generated via complete reconstruction during electrolysis and the high-valence Fe and Ni in the FeNiS-R interface are the real active sites for high OER activity. The reconstructed FeNiS-R exhibits a small overpotential of 290 mV at 100 mA cm−2 and favorable durability (≥80 h), much superior to commercial benchmark IrO2. This work provides a promising avenue to achieve the deep reconstruction of TMSs and the targeted design of OER catalysts in energy devices.

Designed NiMoC@C and NiFeMo2C@C core-shell nanoparticles for oxygen evolution in alkaline media.

Electrochemical water splitting is one of the most promising and clean ways to produce hydrogen as a fuel. Herein, we present a facile and versatile strategy for synthesizing non-precious transition binary and ternary metal-based catalysts encapsulated in a graphitic carbon shell. NiMoC@C and NiFeMo2C@C were prepared via a simple sol-gel based method for application in the Oxygen Evolution Reaction (OER). The conductive carbon layer surrounding the metals was introduced to improve electron transport throughout the catalyst structure. This multifunctional structure showed synergistic effects, possess a larger number of active sites and enhanced electrochemical durability. Structural analysis indicated that the metallic phases were encapsulated in the graphitic shell. Experimental results demonstrated that the optimal core-shell material NiFeMo2C@C exhibited the best catalytic performance for the OER in 0.5M KOH, reaching a current density of 10mAcm-2 at low overpotential of 292mV for the OER, superior to the benchmark IrO2 nanoparticles. The good performances and stability of these OER electrocatalysts, alongside an easily scalable procedure makes these systems ideal for industrial purposes.