Electrocatalytic Performance For Oxygen Evolution Reaction Research Articles

Tailoring of electrocatalytic oxygen evolution reaction performance of 2D conductive Co-catecholate metal-organic frameworks

Herein, we report the microwave hydrothermal synthesis of highly porous and conductive 2D Co-catecholate MOFs (Co-CATs) in the absence (Co-CAT-WO) and presence (Co-CAT-W) of N-methyl-2-pyrrolidone (NMP) polar solvent, and the study of these Co-CATs as electrocatalysts for oxygen evolution reaction (OER). The OER performance of Co-CAT-WO and Co-CAT-W is compared. The as-synthesized Co-CATs exhibit a 2D layered hexagonal structure. The electrical conductivity of Co-CAT-WO and Co-CAT-W is 6.9 and 5.8 S/m, respectively. The good conductivity and porous structure can initiate charge transport to achieve better OER performance under the 4e--transfer process. The as-prepared Co-CAT-WO and Co-CAT-W, respectively, show an overpotential of 455 and 424 mV at 10 mA/cm2 after performing the durability and chronoamperometry experiments for 13 h in 1 M KOH. From the electrochemical studies, it is apparent that the Co-CAT-W exhibits better OER performance with low overpotential, high current density, and excellent stability over extended cycling. Moreover, the lower HOMO-LUMO gap for Co-CAT-W than that of the Co-CAT-WO endorses its better electrocatalytic activity. The post-OER results show that the Co-CAT-W electrocatalyst acts as a "precatalyst" rather than the original catalyst, and it undergoes electrochemical transformation to metal hydroxide and metal oxyhydroxide after the OER studies, promoting the OER kinetics. The findings of this work offer valuable insights into the synthetic strategies for developing 2D conducting metal-catecholate MOF catalysts for efficient and sustainable OER processes, which is crucial in water splitting for sustainable energy production.

Catalytic properties of Fe-based amorphous alloys with different Mo content after acid corrosion

A series of Fe-based amorphous alloy wires with good formation ability, good flexibility, and a large specific surface area were prepared by the melt quenching method, which can be directly used as a self-supporting electrode for the oxygen evolution reaction (OER) of water electrolysis. By controlling the content of Mo, (Fe0.8Ni0.2)71Mo5P12C10B2 (Mo5), (Fe0.8Ni0.2)71Mo10P12C5B2 (Mo10) and (Fe0.8Ni0.2)71Mo15P10C2B2 (Mo15) alloy wires were prepared. It was found that Mo5 and Mo10 alloys still exhibit a fully amorphous structure, while the main body of Mo15 alloy comprises B2Fe3Ni3 and Mo6Ni6C phases. The electrochemical results showed that Mo15 alloy had the best intrinsic catalytic activity. The OER electrocatalytic performance of Mo15 was further improved by 1 h chemical etching after soaking in 0.5 M HNO3, which showed the overpotential was 239 mV and the Tafel slope was 40.6 mV/dec in 1 M KOH with a current density of 10 mA/cm2.

Enhancing Iron Oxide Electrocatalysis for Efficient Overall Water Splitting: A Study of Tailored Synthesis for Advanced Energy Generation and Storage

ABSTRACTWater splitting, a critical milestone in the development of renewable energy, allows the production of pure hydrogen and oxygen. Iron oxide (Fe2O3), a fundamental component in electrochemical water splitting for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER), offers potential because of its accessibility, low cost, and environmental safety. Herein, to analyze the impact of the methodology on its properties, Fe2O3 was produced in three different ways: freeze‐drying (aerogel) (Fe2O3‐AG), hydrothermal (Fe2O3‐HT), and microwave (Fe2O3‐MW). The Fe2O3‐AG outperformed Fe2O3‐HT and Fe2O3‐MW in most properties which showed improved current and overall water‐splitting efficiency. The resulting materials demonstrated good electrocatalytic performance for both HER and OER in alkaline media, with overpotentials for HER of 204, 235, and 255 mV and overpotentials for OER of 222, 288, and 292 mV for the Fe2O3‐AG, Fe2O3‐HT, and Fe2O3‐MW samples, respectively, at a current density of 10 mA/cm2. The freeze‐drying synthesis process has significant potential as a feasible method for the manufacture of Fe2O3‐based electrocatalysts for water‐splitting applications. This study provides important insights into the influence of electrocatalytic and energy storage properties of Fe2O3 based on the use of different methodologies, that is, hydrothermal, microwave‐assisted, and freeze‐drying. Through that, a more assertive analysis can be made concerning changes in morphology, conductivity, exposure of active area, and electrochemical stability which are crucial for the overall performance, hence providing valuable information and considerations for possible large‐scale applications for energy generation and energy storage.

Rutile-structured high-entropy oxyfluorides: A platform for oxygen evolution catalysis

High-entropy (HE) design provides ample opportunities for accessing catalysts with unique physiochemical properties for advanced energy and environmental applications. Although a variety of multi-cationic high-entropy materials (HEMs) have been identified, HEMs consisted of multiple cationic and anionic elements are still limited. Herein, we present the design and synthesis of a series of rutile-structured high-entropy oxyfluorides (HEOFs), including [RuO2]x[MgMnZnCoF2]y, [MnO2]x[MgMnZnCoF2]y, [MoO2]x[MgMnZnCoF2]y, [SnO2]x[MgMnZnCoF2]y and [TiO2]x[MgMnZnCoF2]y (x:y = 3:1, 2:1, 1:1). All the HEOFs are obtained through mechanochemical alloying rutile-structured oxide and fluoride precursors and the HEOFs inherit the crystal structures of the skeleton oxides. Moreover, the HEOFs exhibit enhanced electrocatalytic oxygen evolution reaction (OER) activity than the corresponding one-element precursors. Typically, the best-performed HEOF [RuO2]3[MgMnZnCoF2]1 catalyst requires an overpotential of 240 mV to achieve a current density of 10 mA cm−2, which is lower than RuO2 (291 mV). More impressively, the specific mass activity of [RuO2]3[MgMnZnCoF2]1 is 537.1 A gRu−1 at 1.55 V (vs RHE), which is ca. 7.6 times that of RuO2 (70.5 A gRu−1). The enhanced electrocatalytic OER performance obtained on [RuO2]3[MgMnZnCoF2]1 is ascribed to the contribution of the different cationic and anionic elements that modulates the electronic structures of the pristine RuO2, which facilitates efficient OER kinetics. This work demonstrates the efficacy of high-entropy design towards approaching excellent catalysts for enhanced electrocatalysis.

Computational screening of transition metal atom doped ZnS and ZnSe nanostructures as promising bifunctional oxygen electrocatalysts.

The design of bifunctional oxygen electrocatalysts showing high catalytic performance for the oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) is of great significance for developing new renewable energy storage and conversion technologies. Herein, based on the first principles calculations, we systematically explored the electrocatalytic activity of a series of transition metal atom (Fe, Co, Ni, Cu, Pd and Pt)-doped ZnS and ZnSe nanostructures for OER and ORR. The calculated results revealed that Ni- and Pt-doped ZnS and ZnSe nanostructures exhibit promising electrocatalytic performance for both OER and ORR in comparison to the pristine ZnS and ZnSe nanostructures. Especially, the OER/ORR overpotentials of Ni-doped ZnS and ZnSe nanostructures are estimated to be 0.28/0.30 and 0.31/0.31 V, respectively, disclosing their great potential as bifunctional oxygen electrocatalysts. Moreover, it is found that Ni-doped ZnS and ZnSe nanostructures for OER and ORR are on the top of the volcano plots, evincing promising catalytic performance. Our results provide theoretical insights into a feasible strategy to synthesize highly efficient ZnS- and ZnSe-based bifunctional oxygen electrocatalysts in the future.

Surface reconstruction of defect-engineered MIL-88@Fe2O3 p-n heterojunction for enhanced electrocatalytic water and urea oxidation

Defective p-n heterojunction engineering has been under the spotlighted as a promising strategy for electrochemical oxygen evolution reaction (OER) and urea oxidation reaction (UOR). Still, it remains a great challenge how to use the space-charge region of p-n heterojunction to study the regulation mechanism of the p-n heterogeneous interface and vacancy defects on the incomplete self-reconstruction from pristine materials to (oxy)hydroxides. Herein, NH2-MIL-88b(Fe)/α-Fe2O3 p-n heterojunction with rich oxygen vacancies (denoted as p-n MIL-88@Fe2O3-OV) has been prepared using a simple one-step solvothermal method. The prepared catalyst exhibits promising electrocatalytic performance for OER and UOR, requiring low potentials of 1.50 and 1.35 V to reach the current density of 10 mA cm−2, respectively. The combined in-situ/ex-situ experimental and theoretical investigations unveil that p-n heterojunction engineering can not only facilitate charge transfer from n-type α-Fe2O3 to p-type NH2-MIL-88b(Fe) (denoted as MIL-88) and generate abundant oxygen vacancies, but also appreciably trigger phase transformation of MIL-88 into active FeOOH. The reconstructed FeOOH/α-Fe2O3 heterojunction optimizes the bonding strength towards key oxygen-containing intermediates and boosts the intrinsic activity. This work provides new insight into the self-reconstruction effect in the p-n heterojunction for enhancing the OER and UOR catalytic activity.

High-entropy amorphous FeCoCrNi thin films with excellent electrocatalytic oxygen evolution reaction performance

High-entropy amorphous FeCoCrNi thin-film catalysts with different Cr contents were prepared on the surface of copper substrate via electrodeposition. Their electrocatalytic performance for oxygen evolution reaction (OER) in alkaline solution was investigated. The catalyst with the optimal performance was obtained when the concentration of Cr3+ in the electrodeposition solution was 200 g/L. It achieved a current density of 10 mA⸱cm−2 with a low overpotential of merely 295 mV and demonstrated a Tafel slope of 69.52 mV⸱dec−1, indicating favorable reaction kinetics. Furthermore, this catalyst showed remarkable stability, maintaining its catalytic performance after 1000 cycles of cyclic voltammetry tests in the alkaline solution. The reasons for its excellent catalytic performance are as follows: (1) The uniform cracks and cellular structure on the film surface result in a larger active area; (2) The amorphous structure is more prone to surface reconstruction during the catalytic process, exposing more active sites; (3) Cr element regulates the valence states of Fe and Co ions as well as the existence forms of Ni and Co elements during the catalytic process, which accelerates the OER process and improves the catalytic performance.

Unraveling the Dynamic Reconstruction of Active Co(IV)-O Sites on Ultrathin Amorphous Cobalt-Iron Hydroxide Nanosheets for Efficient Oxygen-Evolving.

Highly-efficient and cost-effective electrocatalysts toward the oxygen evolution reaction (OER) are crucial for advancing sustainable energy technologies. Herein, a novel approach leveraging corrosion engineering is presented to facilitate the in situ growth of amorphous cobalt-iron hydroxides on nickel-iron foam (CoFe(OH)x-m/NFF) within a NaCl-CoCl2 aqueous solution. By adjusting the concentration of the solution, the compositions can tailored and morphologies of these hydroxides to optimize the OER electrocatalytic performance. Specifically, the CoFe(OH)x-500/NFF electrode manifests as distinctive 3D flower-like clusters composed of remarkably thin nanosheets, measuring a mere 1nm in thickness. By virtue of the amorphous and ultrathin nanosheet structure, the CoFe(OH)x-500/NFF electrode exhibits superior OER activity, characterized by notably low overpotentials (η100, 274mV) and an exceptionally small Tafel slope of 40.54mV dec-1. Moreover, the electrode's performance remains robust, maintaining low overpotentials for 168h at 100mA cm-2. In situ Raman spectroscopy indicates that the hydroxides experience surface structural reconstruction and transform into high-valent CoFeO2 with active Co(IV)-O sites during the OER. Theoretical calculations underscore the critical role of the NiFe substrate in enhancing the electrode's OER activity by improving electrical conductivity and modifying the adsorption energy of reaction intermediates, thereby reducing the energy barrier for the reaction.

NiCo-LDH sheets and Ag3PO4 nanoparticles decorated on graphitic carbon nitride for efficient oxygen evolution reaction

Ternary heterostructure engineering enables highly efficient interfacial charge transfer, which can enhance the efficiency of electrocatalysts for the oxygen evolution reaction (OER), and has thus attracted widespread interest in electrocatalysis. NiCo-LDH/CN/AgPO was synthesized via ultrasonication and subjected to morphological analyses using X-ray diffraction, scanning electron microscopy, and (high-resolution) transmission electron microscopy. The synergistic effects in the ternary heterostructured NiCo-LDH/CN/AgPO nanocomposite comprising 2D nickel-cobalt layered double hydroxide (NiCo-LDH) and silver phosphate (Ag3PO4) nanospecies anchored on graphitic carbon nitride (g-C3N4) nanosheets will provide promising features as an electrode for the alkaline oxygen evolution reaction (OER). The NiCo-LDH/CN/AgPO heterostructure demonstrated exceptional electrocatalytic OER performance compared to AgPO/NiCo-LDH, AgPO/CN, and CN, achieving a low overpotential of 289 mV for the OER at 10 mA cm−2 in 1.0 M KOH. This superior catalytic activity is attributed to the relatively large electroactive surface area, rapid charge transfer capability, and intimate interactions between the components. The innovative design and synthesis of the NiCo-LDH/CN/AgPO heterostructure provide significant potential for constructing electrocatalysts with superior efficacy in oxygen evolution reactions.

Enhanced hydrogen production via catalytic water and urea oxidation in a hybrid acid-base electrolytic cell with NiFe-LDH/NiMoO4/NF

The construction of crystalline-amorphous coupling structure is one of the effective strategies to enhance the performance of oxygen evolution reaction (OER) and urea oxidation reaction (UOR). Herein, NiFe-LDH/NiMoO4/NF with high oxygen evolution and urea oxidation performance was successfully prepared by electrodeposition of amorphous substances on the crystalline precursor of hydrothermal synthesis. Remarkably, the NiFe-LDH/NiMoO4/NF displays exceptional electrocatalytic performance for OER and UOR, with a potential of only 1.57 V vs. RHE at 100 mA cm−2 and the Tafel slope of 54.4 mV dec−1 for OER, high UOR activity with a potential of 1.45 mV@100 mA cm−2 and the Tafel slope of 20.4 mV dec−1 in 1.0 M KOH with 0.33 M urea solution. In a hybrid acid-base electrolysis system for urea oxidation-assisted H2 production using NiFe-LDH/NiMoO4/NF as the anode electrode and Pt/C/NF as the cathode electrode, the process requires a cell voltage of only 0.55 V vs. RHE at 10 mA cm−2. Moreover, this hybrid acid/base system demonstrates stable operation for 110 h with minimal attenuation at a current density of 100 mA cm−2. These results indicate a facile strategy for the design of electrodes with crystalline-amorphous coupling structures for energy conversion.

Structural optimization: Ternary FeNiZn sulfide nanoparticles anchored on nanosheets to strengthen oxygen evolution reaction

Enhancing the activity of oxygen evolution reaction (OER) is crucial for improving the efficiency of electrochemical water splitting (EWS). The highly adjustable electronic structure and potential high conductivity of transition metal sulfides (TMSs) make them promising candidates for OER electrocatalysts. Herein, we have synthesized trimetallic sulfides Fe2Ni1Zn1–S(II) based on layered double hydroxides (LDHs) precursor employing a facile and efficient two-step solvothermal approach. Benefitting from the multi-metallic synergistic effect and the distinctive interfacial structure, Fe2Ni1Zn1–S(II) shows excellent electrocatalytic OER performance (η10 = 252 mV, Tafel slope = 64.2 mV∙dec−1). Meanwhile, it has outstanding stability (50 h) in 1 M KOH, which is better than RuO2 and many other metal sulfide electrocatalysts. Furthermore, it was found that the structure of the catalyst was still retained after OER test, which further verified its catalytic stability. This work supplies an effective route for the preparation of LDHs derived multi-metallic sulfides.

Ultrathin high-entropy layered double hydroxide electrocatalysts for enhancing oxygen evolution reaction

At the heart of the oxygen evolution reaction (OER), the properties of electrocatalysts play a crucial role in determining reaction efficiency. This underscores the need to design and develop highly effective OER electrocatalysts. The unique layer structure and electronic properties make layer double hydroxide (LDH) a promising candidate for driving OER electrocatalysis. Furthermore, high-entropy materials (HEMs) exhibit core effects such as high entropy, lattice distortion, sluggish diffusion, and cocktail effect, which can enhance active sites and optimize binding energy with intermediates. Combining the advantages of these two material categories, we propose the synthesis of high-entropy layered double hydroxides (HE-LDHs) through a straightforward MOF-mediated synthesis method to showcase exceptional electrocatalytic OER performance. Detailed mechanistic studies have shown that its outstanding performance stems from its ultrathin structure and the inherent activity of a high-entropy material that promotes charge transfer, mass transport, and the evolution of reaction intermediates.

Electronic-Structure Transformation of Platinum-Rich Nanowires as Efficient Electrocatalyst for Overall Water Splitting.

Platinum (Pt) has been widely used as cathodic electrocatalysts for the hydrogen evolution reaction (HER) but unfortunately neglected as an anodic electrocatalyst for the oxygen evolution reaction (OER) due to excessively strong bonding with oxygen species in water splitting electrolyzers. Herein we report that fine control over the electronic-structure and local-coordination environment of Pt-rich PtPbCu nanowires (NWs) by doping of iridium (Ir) lowers the overpotential of the OER and simultaneously suppresses the overoxidation of Pt in IrPtPbCu NWs during water electrolysis. In light of the one-dimensional morphology featured with atomically dispersed IrOx species and electronically modulated Pt-sites, the IrPtPbCu NWs exhibit an enhanced OER (175 mV at 10 mA cm-2) and HER (25 mV at 10 mA cm-2) electrocatalytic performance in acidic media and yield a high turnover frequency. For OER at the overpotential of 250 mV, the IrPtPbCu NWs show an enhanced mass activity of 1.51 A mg-1Pt+Ir (about 19 times higher) than Ir/C. For HER at the overpotential of 50 mV, NWs exhibit a remarkable mass activity of 1.35 A mg-1Pt+Ir, which is 2.6-fold relative to Pt/C. Experimental results and theoretical calculations corroborate that the doping of Ir in NWs has the capacity to suppress the formation of Ptx>4 derivates and ameliorate the adsorption free energy of reaction intermediates during the water electrolysis. This approach enabled the realization of a previously unobserved mechanism for anodic electrocatalysts.

Enhancing Oxygen Evolution Reaction Performance of Metal-Organic Frameworks through Cathode Activation.

Due to their abundant active sites and porous structures, metal-organic frameworks (MOFs) have garnered significant interest as oxygen evolution reaction (OER) electrocatalysts. Nevertheless, the development of MOF-based electrocatalysts with efficient OER activity and excellent stability simultaneously still faces challenges. Herein, a cathodic activation strategy was used to enhance the OER electrocatalytic performance of M-HHTP for the first time, where M refers to Ni, Cu, Co, Fe, while HHTP denotes 2, 3, 6, 7, 10, 11-hexahydroxytriphenylene. As a prototype, the activated Ni-HHTP (HA-Ni-HHTP) demonstrates outstanding OER performance, with an overpotential as low as 140 mV at 20 mA cm-2 and a small Tafel slope of 78.7 mV-1, surpassing commercial RuO2 and rivaling state-of-the-art MOFs-based electrocatalysts. Characterizations and density functional theory calculations reveal that the superior performance of HA-Ni-HHTP is primarily ascribed to changes in semiconductor type, contact angle, and oxygen vacancy content induced by cathodic activation. Electrochemical impedance spectroscopy analysis using the transmission line model confirms that cathodic activation accelerates charge transport, enhancing the OER process. Furthermore, the cathodic activation strategy holds promise for improving the water oxidation performance of other MOFs such as Fe-HHTP, Co-HHTP, and Cu-HHTP.

Facile top-down fabrication of integrated amorphous NiFe-based electrocatalytic electrodes for high current and long-life oxygen evolution

Developing an industrially relevant electrode with high catalytic activity, stability, and tunable composition/size for large-scale water electrolysis is a significant challenge. We have created an integrated electrode (NFM30-N) for the oxygen evolution reaction (OER) using a facile top-down approach that combines arc melting with dealloying-oxidation. Due to the dealloying-oxidation effect, the as-derived porous amorphous M–O, M–OH, and M–OOH (M = Ni, Fe) nanocones cover the basic NiFeMn alloy. This integrated design enables NFM30-N to exhibit outstanding OER performance at high current densities, requiring low overpotentials of only 282 and 323 mV to achieve large current densities of 100 and 500 mA cm−2, respectively. It also displays a small Tafel slope of 44.1 mV dec−1 and remarkable stability for over 100 h at 100 and 500 mA cm−2. When used as an anode, a two-electrode electrolyzer cell with NFM30-N at 500 mA cm−2 only requires a cell voltage of 1.619 V and exhibits excellent stability, with almost no performance degradation after continuous chronopotentiometry test for each 100 h at 500 and 100 mA cm−2. This exceptional OER electrocatalytic performance is attributed to the integrated structure providing high electrical conductivity and stability, the presence of numerous active sites due to dealloying and the amorphous structure, and the promotion of the OER process by M–O, M–OH, and M–OOH species. This work offers a novel idea for fabricating integrated, industrially relevant electrocatalytic electrodes through traditional metallurgy combined with dealloying-oxidation.

Manganese-decorated CoP@CoFe2O4 nanorod arrays for high-efficiency alkaline water oxidation

Regulating the intrinsic activity of electrocatalysts is an effective strategy towards outstanding behaviour for oxygen evolution reaction (OER). Herein, the rational design of a Mn–CoP@CoFe2O4 core-shell heterojunction using nickel foam (NF) as a supporting material with special interface engineering has been investigated by a facile hydrothermal technique combined with phosphorization and electrodeposition method. The physical characterization demonstrates Mn–CoP@CoFe2O4 core-shell heterostructure with Mn–CoP nanoneedles as core and CoFe2O4 nanosheets as shell has been successfully acquired. The electrochemical measurements of the as-prepared Mn–CoP@CoFe2O4/NF core-shell heterojunction nanoarray electrode exhibit the superior electrocatalytic behaviour for OER (Tafel slope of 35.6 mV dec−1 and overpotential of 209.6 mV@10 mA cm−2). The remarkable OER behaviour may be ascribed to the sufficient active sites and the enhanced intrinsic activity due to the introduction of CoFe2O4 and Mn element, which can regulate the electron structure and increase the turnover frequency. Furthermore, the Mn–CoP@CoFe2O4/NF electrode appears an excellent long-run stability during the OER process at 100 mA cm−2 for 100 h. Therefore, the construction of metal doping transition metal-based core-shell heterostructure electrocatalysts may be a promising way for the remarkable OER electrocatalytic performance towards water splitting.

Enhance the performance of OER electrocatalyst via synergistic oxygen vacancies and NiFe2O4-phosphorene heterostructure

The exfoliated black phosphorus nanosheets (EBP, phosphorene) is considered as a highly anticipated electrocatalyst for oxygen evolution reaction (OER) because of its unique electron structure. However, the poor stability and conductivity of EBP limit its application potential. In this paper, a heterostructure of EBP and nickel ferrite with oxygen vacancies (NFO-V-EBP) is designed by using a simple ultrasound and electronic regulation of EBP. NFO-V forms P-Ni bonds and P-O-M (M=Ni/Fe) bonds by interacting with the active lone pair electrons on the surface of EBP, which passivates EBP to improve its stability and provide more active sites. In situ Raman testing is used to assist in demonstrating the cooperative effect of EBP and oxygen vacancy, which reduced the potential barrier of OER reaction. NFO-V-EBP heterostructure exhibits excellent electrocatalytic performance for alkaline OER, showing overpotential of 243 mV at current density of 10 mA cm-2 and Tafel slope of 39 mV dec-1. It also has excellent long-term stability, at a density of 10 mA cm-2 with no significant increase in overpotential observed after nearly 100 hours under the chronoamperometric method.

Self-Assembled Conjugated Coordination Polymer Nanorings: Role of Morphology and Redox Sites for the Alkaline Electrocatalytic Oxygen Evolution Reaction.

Electrocatalytic water splitting provides a sustainable method for storing intermittent energies, such as solar energy and wind, in the form of hydrogen fuel. However, the oxygen evolution reaction (OER), constituting the other half-cell reaction, is often considered the bottleneck in overall water splitting due to its slow kinetics. Therefore, it is crucial to develop efficient, cost-effective, and robust OER catalysts to enhance the water-splitting process. Transition-metal-based coordination polymers (CPs) serve as promising electrocatalysts due to their diverse chemical architectures paired with redox-active metal centers. Despite their potential, the rational use of CPs has faced obstacles including a lack of insights into their catalytic mechanisms, low conductivity, and morphology issues. Consequently, achieving success in this field requires the rational design of ligands and topological networks with the desired electronic structure. This study delves into the design and synthesis of three novel conjugated coordination polymers (CCPs) by leveraging the full conjugation of terpyridine-attached flexible tetraphenylethylene units as electron-rich linkers with various redox-active metal centers [Co(II), Ni(II), and Zn(II)]. The self-assembly process is tuned for each CCP, resulting in two distinct morphologies: nanosheets and nanorings. The electrocatalytic OER performance efficiency is then correlated with factors such as the nanostructure morphology and redox-active metal centers in alkaline electrolytes. Notably, among the three morphologies studied, nanorings for each CCP exhibit a superior OER activity. Co(II)-integrated CCPs demonstrate a higher activity between the redox-active metal centers. Specifically, the Co(II) nanoring morphology displays exceptional catalytic activity for OER, with a lower overpotential of 347 mV at a current density of 10 mA cm-2 and small Tafel slopes of 115 mV dec-1. The long-term durability is demonstrated for at least 24 h at 1.57 V vs RHE during water splitting. This is presumably the first proof that links the importance of nanostructure morphologies to redox-active metal centers in improving the OER activity, and it may have implications for other transdisciplinary energy-related applications.

Self-supported low-crystallinity CoFe layered double hydroxide nanospheres on monolayer Ti3C2 electrode for oxygen evolution reaction

The electrocatalytic oxygen evolution reaction is a crucial means to support the conversion and storage of the sustainable renewable energy. Low-crystallinity can offer short-range structural ordering and high active site density. In this work, an efficient self-supported oxygen evolution reaction (OER) electrocatalyst, cobalt iron layered double hydroxide (LDH) grown on Ti3C2 modified nickel foam (NF) heterostructure anode (CoFe-LDH/Ti3C2/NF) was prepared using electrodeposition. The exceptional electrocatalytic OER performance is ensured by in situ decorating monolayer Ti3C2/NF (s-Ti3C2/NF) with low-crystallinity CoFe nanospheres. By harnessing the low crystallinity, well-chosen composition and reasonable heterostructure, the overpotential of CoFe-LDH/Ti3C2/NF decreases to 246 mV at a current density of 10 mA·cm−2 in alkaline media. After 3000 cyclic voltammograms cycles, the ignorable increase in overpotential of 14 mV suggest the excellent long circular stability. Moreover, an accelerated reaction kinetics is implied by the smaller Tafel slope (28.76 mV·dec−1) and higher double-layer specific capacitance (2.33 mF·cm−2), which surpassed the counterparts CoFe-LDH grown on NF (CoFe-LDH/NF) and s-Ti3C2/NF. This work paves a new way to fabricate the low-crystallinity materials for electrocatalysis and energy storage.

Self-supported monometallic FeS2/FeOOH-ZnO@NF with abundant oxygen vacancies as efficient and stable electrocatalysts for the OER and HER

The construction of heterogeneous interfaces and oxygen vacancy (Ov) is a very useful method to enhance the catalytic activity performance of catalysts. In this work, the high-performance a monometallic iron based bifunctional electrocatalyst FeS2/FeOOH-ZnO@NF with oxygen vacancy (Ov) and heterogeneous interface is prepared by the ZnO template induced deposition method for the first time. Due to the synergistic effect of the heterogeneous interface of FeS2/FeOOH-ZnO@NF and the oxygen vacancies of the ZnO, the FeS2/FeOOH-ZnO@NF catalysts exhibited excellent hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) activity in alkaline media, with a low overpotential of 74 mV and 177 mV at 10 mA cm−2, respectively. It should be emphasized that the FeS2/FeOOH-ZnO@NF || FeS2/FeOOH-ZnO@NF electrolytic cell has an ultra-low decomposition voltage, only 1.41 V at 10 mA cm−2 and 1.49 V at 20 mA cm−2, which is much lower than that currently reported in most literatures. This work will provide a new strategy and idea for the improvement of HER and OER electrocatalytic performance of transition metal-based catalyst.