Amorphous P-CoOX Promotes the Formation of Hypervalent Ni Species in NiFe LDHs by Amorphous/Crystalline Interfaces for Excellent Catalytic Performance of Oxygen Evolution Reaction.

Water electrolysis has become an attractive hydrogen production method. Oxygen evolution reaction (OER) is a bottleneck of water splitting as its four-electron transfer procedure presents sluggish reaction kinetics. Designing composite catalysts with high performance for efficient OER still remains a huge challenge. Here, the P-doped cobalt oxide/NiFe layered double hydroxides (P-CoOX/NiFe LDHs) composite catalysts with amorphous/crystalline interfaces are successfully prepared for OER by hydrothermal-electrodeposition combined method. The results of electrochemical characterizations, operando Raman spectra, and DFT theoretical calculations have demonstrated the electrons in the P-CoOX/NiFe LDHs heterointerfaces are easily transferred from Ni2+ to Co3+ because that the amorphous configuration of P-CoOX can well induce Ni-O-Co orbital coupling. The electron transfer of Ni2+ to the surrounding Fe3+ and Co3+ will lead to the unoccupied eg orbitals of Ni3+ that can promote water dissociation and accelerate *OOH migration to improve OER catalytic performance. The optimized P-CoOX/NiFe LDHs exhibit superior catalytic performance for OER with a very low overpotential of 265 mV at 300 mA cm-2 and excellent long-term stability of 500 h with almost no attenuation at 100 mA cm-2. This work will provide a new method to design high-performance NiFe LDHs-based catalysts for OER.

High-Performance Bifunctional Electrocatalysts for Flexible and Rechargeable Zn-Air Batteries: Recent Advances.

Flexible rechargeable Zn-air batteries (FZABs) exhibit high energy density, ultra-thin, lightweight, green, and safe features, and are considered as one of the ideal power sources for flexible wearable electronics. However, the slow and high overpotential oxygen reaction at the air cathode has become one of the key factors restricting the development of FZABs. The improvement of activity and stability of bifunctional catalysts has become a top priority. At the same time, FZABs should maintain the battery performance under different bending and twisting conditions, and the design of the overall structure of FZABs is also important. Based on the understanding of the three typical configurations and working principles of FZABs, this work highlights two common strategies for applying bifunctional catalysts to FZABs: 1) powder-based flexible air cathode and 2) flexible self-supported air cathode. It summarizes the recent advances in bifunctional oxygen electrocatalysts and explores the various types of catalyst structures as well as the related mechanistic understanding. Based on the latest catalyst research advances, this paper introduces and discusses various structure modulation strategies and expects to guide the synthesis and preparation of efficient bifunctional catalysts. Finally, the current status and challenges of bifunctional catalyst research in FZABs are summarized.

Fe-Doped Ni2P/NiSe2 Composite Catalysts for Urea Oxidation Reaction (UOR) for Energy-Saving Hydrogen Production by UOR-Assisted Water Splitting.

The development of efficient urea oxidation reaction (UOR) catalysts helps UOR replace the oxygen evolution reaction (OER) in hydrogen production from water electrolysis. Here, we prepared Fe-doped Ni2P/NiSe2 composite catalyst (Fe-Ni2P/NiSe2-12) by using phosphating-selenizating and acid etching to increase the intrinsic activity and active areas. Spectral characterization and theoretical calculations demonstrated that electrons flowed through the Ni-P-Fe-interface-Ni-Se-Fe, thus conferring high UOR activity to Fe-Ni2P/NiSe2-12, which only needed 1.39 V vs RHE to produce the current density of 100 mA cm-2. Remarkably, this potential was 164 mV lower than that required for the OER under the same conditions. Furthermore, EIS demonstrated that UOR driven by the Fe-Ni2P/NiSe2-12 exhibited faster interfacial reactions, charge transfer, and current response compared to OER. Consequently, the Fe-Ni2P/NiSe2-12 catalyst can effectively prevent competition with OER and NSOR, making it suitable for efficient hydrogen production in UOR-assisted water electrolysis. Notably, when water electrolysis is operated at a current density of 40 mA cm-2, this UOR-assisted system can achieve a decrease of 140 mV in the potential compared to traditional water electrolysis. This study presents a novel strategy for UOR-assisted water splitting for energy-saving hydrogen production.

Co/Co3O4 Heterojunctions Encased in Porous N-Doped Carbon Nanocapsules for High-Performance Cathode of Rechargeable Zinc-Air Batteries.

A long-term goal of rechargeable zinc-air batteries (ZABs) has always been to design bifunctional electrocatalysts that are robust, effective, and affordable for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER). It has become a feasible method to construct metal/metal oxide interfaces to achieve superior electrocatalytic performance for ORR and OER by enhanced charge transfer. In this study, Co/Co3O4 heterojunctions were successfully prepared and encased in porous N-doped mesoporous carbon (Co/Co3O4@NC) via a simple condensation-carbonization-etching method. The extensive specific surface area of Co/Co3O4@NC facilitates effective interaction between the electrolyte and the catalyst, thereby enabling sufficient exposure of active sites for the ORR and the OER, consequently enhancing the rate of transport of active species. The well-designed Co/Co3O4@NC delivers superior ORR catalytic activity with a half-wave potential of 0.82 V (vs RHE) and a low overpotential of 347 mV at 10 mA cm-2 for OER in alkaline solution. The power density of Co/Co3O4@NC-based alkaline aqueous ZAB (156.5 mW cm-2) is superior to the commercial Pt/C + IrO2-based alkaline aqueous ZAB, and the cycling stability of ZAB is up to 220 h. In addition, Co/Co3O4@NC-based ZAB shows a high power density (50.1 mW cm-2). The construction of metal/metal oxide heterojunction encased in N-doped mesoporous carbon provides a novel route for the design of bifunctional electrocatalysts for high-performance ZABs.

Modulation Strategies for the Preparation of High-Performance Catalysts for Urea Oxidation Reaction and Their Applications.

Compared with the traditional electrolysis of water to produce hydrogen, urea-assisted electrolysis of water to produce hydrogen has significant advantages and has received extensive attention from researchers. Unfortunately, urea oxidation reaction (UOR) involves a complex six-electron transfer process leading to high overpotential, which forces researchers to develop high-performance UOR catalysts to drive the development of urea-assisted water splitting. Based on the UOR mechanism and extensive literature research, this review summarizes the strategies for preparing highly efficient UOR catalysts. First, the UOR mechanism is introduced and the characteristics of excellent UOR catalysts are pointed out. Aiming at this, the following modulation strategies are proposed to improve the catalytic performance based on summarizing various literature: 1) Accelerating the active phase formation to reduce initial potential; 2) Creating double active sites to trigger a new UOR mechanism; 3) Accelerating urea adsorption and promoting C─N bond cleavage to ensure the effective conduct of UOR; 4) Promoting the desorption of CO2 to improve stability and prevent catalyst poisoning; 5) Promoting electron transfer to overcome the inherent slow dynamics of UOR; 6) Increasing active sites or active surface area. Then, the application of UOR in electrochemical devices is summarized. Finally, the current deficiencies and future directions are discussed.

Interfacial Fe-O-Ni-O-Fe Bonding Regulates the Active Ni Sites of Ni-MOFs via Iron Doping and Decorating with FeOOH for Super-Efficient Oxygen Evolution.

The integration of Fe dopant and interfacial FeOOH into Ni-MOFs [Fe-doped-(Ni-MOFs)/FeOOH] to construct Fe-O-Ni-O-Fe bonding is demonstrated and the origin of remarkable electrocatalytic performance of Ni-MOFs is elucidated. X-ray absorption/photoelectron spectroscopy and theoretical calculation results indicate that Fe-O-Ni-O-Fe bonding can facilitate the distorted coordinated structure of the Ni site with a short nickel-oxygen bond and low coordination number, and can promote the redistribution of Ni/Fe charge density to efficiently regulate the adsorption behavior of key intermediates with a near-optimal d-band center. Here the Fe-doped-(Ni-MOFs)/FeOOH with interfacial Fe-O-Ni-O-Fe bonding shows superior catalytic performance for OER with a low overpotential of 210 mV at 15 mA cm-2 and excellent stability with ≈3 % attenuation after a 120 h cycle test. This study provides a novel strategy to design high-performance Ni/Fe-based electrocatalysts for OER in alkaline media.

Surface-Adsorbed Carboxylate Ligands on Layered Double Hydroxides/Metal-Organic Frameworks Promote the Electrocatalytic Oxygen Evolution Reaction.

Metal-organic frameworks (MOFs) with carboxylate ligands as co-catalysts are very efficient for the oxygen evolution reaction (OER). However, the role of local adsorbed carboxylate ligands around the in-situ-transformed metal (oxy)hydroxides during OER is often overlooked. We reveal the extraordinary role and mechanism of surface-adsorbed carboxylate ligands on bi/trimetallic layered double hydroxides (LDHs)/MOFs for OER electrocatalytic activity enhancement. The results of X-ray photoelectron spectroscopy (XPS), synchrotron X-ray absorption spectroscopy, and density functional theory (DFT) calculations show that the carboxylic groups around metal (oxy)hydroxides can efficiently induce interfacial electron redistribution, facilitate an abundant high-valence state of nickel species with a partially distorted octahedral structure, and optimize the d-band center together with the beneficial Gibbs free energy of the intermediate. Furthermore, the results of in situ Raman and FTIR spectra reveal that the surface-adsorbed carboxylate ligands as Lewis base can promote sluggish OER kinetics by accelerating proton transfer and facilitating adsorption, activation, and dissociation of hydroxyl ions (OH- ).

Efficient Hydrogen Evolution on Cu Nanodots-Decorated Ni3S2 Nanotubes by Optimizing Atomic Hydrogen Adsorption and Desorption.

Low-cost transition-metal dichalcogenides (MS2) have attracted great interest as alternative catalysts for hydrogen evolution. However, a significant challenge is the formation of sulfur-hydrogen bonds on MS2 (S-Hads), which will severely suppress hydrogen evolution reaction (HER). Here we report Cu nanodots (NDs)-decorated Ni3S2 nanotubes (NTs) supported on carbon fibers (CFs) (Cu NDs/Ni3S2 NTs-CFs) as efficient electrocatalysts for HER in alkaline media. The electronic interactions between Cu and Ni3S2 result in Cu NDs that are positively charged and can promote water adsorption and activation. Meanwhile, Ni3S2 NTs are negatively charged and can weaken S-Hads bonds formed on catalyst surfaces. Therefore, the Cu/Ni3S2 hybrids can optimize H adsorption and desorption on electrocatalysts and can promote both Volmer and Heyrovsky steps of HER. The strong interactions between Cu and Ni3S2 cause the Cu NDs/Ni3S2 NTs-CFs electrocatalysts to exhibit the outstanding HER catalytic performance with low onset potential, high catalytic activity, and excellent stability.

Pt-like Hydrogen Evolution Electrocatalysis on PANI/CoP Hybrid Nanowires by Weakening the Shackles of Hydrogen Ions on the Surfaces of Catalysts.

The search for high active, stable, and cost-efficient hydrogen evolution reaction (HER) electrocatalysts for water electrolysis has attracted great interest. The coordinated water molecules in the hydronium ions will obviously reduce the positive charge density of H+ and hamper the ability of H+ to receive electrons from the cathode, leading to large overpotential of HER on nonprecious metal catalysts. Here we realize Pt-like hydrogen evolution electrocatalysis on polyaniline (PANI) nanodots (NDs)-decorated CoP hybrid nanowires (HNWs) supported on carbon fibers (CFs) (PANI/CoP HNWs-CFs) as PANI can effectively capture H+ from hydronium ions to form protonated amine groups that have higher positive charge density than those of hydronium ions and can be electro-reduced easily. The PANI/CoP HNWs-CFs as low-cost electrocatalysts show excellent catalytic performance toward HER in acidic solution, such as super high catalytic activity, small Tafel slope, and superior stability.

Activating CoOOH Porous Nanosheet Arrays by Partial Iron Substitution for Efficient Oxygen Evolution Reaction.

Iron-substituted CoOOH porous nanosheet arrays grown on carbon fiber cloth (denoted as Fex Co1-x OOH PNSAs/CFC, 0≤x≤0.33) with 3D hierarchical structures are synthesized by in situ anodic oxidation of α-Co(OH)2 NSAs/CFC in solution of 0.01 m (NH4 )2 Fe(SO4 )2 . X-ray absorption fine spectra (XAFS) demonstrate that CoO6 octahedral structure in CoOOH can be partially substituted by FeO6 octahedrons during the transformation from α-Co(OH)2 to Fex Co1-x OOH, and this is confirmed for the first time in this study. The content of Fe in Fex Co1-x OOH, no more than 1/3 of Co, can be controlled by adjusting the in situ anodic oxidation time. Fe0.33 Co0.67 OOH PNSAs/CFC shows superior OER electrocatalytic performance, with a low overpotential of 266 mV at 10 mA cm-2 , small Tafel slope of 30 mV dec-1 , and high durability.

Efficient Hydrogen Evolution Electrocatalysis Using Cobalt Nanotubes Decorated with Titanium Dioxide Nanodots.

TiO2 Co nanotubes decorated with nanodots (TiO2 NDs/Co NSNTs-CFs) are reported as high-performance earth-abundant electrocatalysts for the hydrogen evolution reaction (HER) in alkaline solution. TiO2 NDs/Co NSNTs can promote water adsorption and optimize the free energy of hydrogen adsorption. More importantly, the absorbed water can be easily activated in the presence of the TiO2 -Co hybrid structure. These advantages will significantly promote HER. TiO2 NDs/Co NSNTs-CFs as electrocatalysts show a high catalytic performance towards HER in alkaline solution. This study will open up a new avenue for designing and fabricating low-cost high-performance HER catalysts.

Silica-Polypyrrole Hybrids as High-Performance Metal-Free Electrocatalysts for the Hydrogen Evolution Reaction in Neutral Media.

Constructing inorganic-organic hybrids with superior properties in terms of water adsorption and activation will lead to catalysts with significantly enhanced electrocatalytic activity in the hydrogen evolution reaction (HER) in environmentally benign neutral media. Herein, we report SiO2 -polypyrrole (PPy) hybrid nanotubes supported on carbon fibers (CFs) (SiO2 /PPy NTs-CFs) as inexpensive and high-performance electrocatalysts for the HER in neutral media. Because of the strong electronic interactions between SiO2 and PPy, the SiO2 uniquely serves as the centers for water adsorption and activation, and accordingly promotes the HER. The metal-free SiO2 /PPy NTs-CFs displayed high catalytic activity in the HER in neutral media, such as a low onset potential and small Tafel slope, as well as excellent long-term durability.

An Alkaline-Stable, Metal Hydroxide Mimicking Metal-Organic Framework for Efficient Electrocatalytic Oxygen Evolution.

Postsynthetic ion exchange of [Co2(µ-Cl)2(btta)] (MAF-X27-Cl, H2bbta =1H,5H-benzo(1,2-d:4,5-d')bistriazole) possessing open metal sites on its pore surface yields a material [Co2(µ-OH)2(bbta)] (MAF-X27-OH) functionalized by both open metal sites and hydroxide ligands, giving drastically improved electrocatalytic activities for the oxygen evolution reaction (an overpotential of 292 mV at 10.0 mA cm(-2) in 1.0 M KOH solution). Isotope tracing experiments further confirm that the hydroxide ligands are involved in the OER process to provide a low-energy intraframework coupling pathway.

FeOOH/Co/FeOOH Hybrid Nanotube Arrays as High-Performance Electrocatalysts for the Oxygen Evolution Reaction.

Herein, we developed FeOOH/Co/FeOOH hybrid nanotube arrays (HNTAs) supported on Ni foams for oxygen evolution reaction (OER). The inner Co metal cores serve as highly conductive layers to provide reliable electronic transmission, and can overcome the poor electrical conductivity of FeOOH efficiently. DFT calculations demonstrate the strong electronic interactions between Co and FeOOH in the FeOOH/Co/FeOOH HNTAs, and the hybrid structure can lower the energy barriers of intermediates and thus promote the catalytic reactions. The FeOOH/Co/FeOOH HNTAs exhibit high electrocatalytic performance for OER, such as low onset potential, small Tafel slope, and excellent long-term durability, and they are promising electrocatalysts for OER in alkaline solution.

Palladium-cobalt nanotube arrays supported on carbon fiber cloth as high-performance flexible electrocatalysts for ethanol oxidation.

PdCo nanotube arrays (NTAs) supported on carbon fiber cloth (CFC) (PdCo NTAs/CFC) are presented as high-performance flexible electrocatalysts for ethanol oxidation. The fabricated flexible PdCo NTAs/CFC exhibits significantly improved electrocatalytic activity and durability compared with Pd NTAs/CFC and commercial Pd/C catalysts. Most importantly, the PdCo NTAs/CFC shows excellent flexibility and the high electrocatalytic performance remains almost constant under the different distorted states, such as normal, bending, and twisting states. This work shows the first example of Pd-based alloy NTAs supported on CFC as high-performance flexible electrocatalysts for ethanol oxidation.

Quantitative Detection of Photothermal and Photoelectrocatalytic Effects Induced by SPR from Au@Pt Nanoparticles.

The surface plasmon resonance (SPR) induced photothermal and photoelectrocatalysis effects are crucial for catalytic reactions in many areas. However, it is still difficult to distinguish these two effects quantitatively. Here we used surface-enhanced Raman scattering (SERS) to detect the photothermal and photoelectrocatalytic effects induced by SPR from Au core Pt shell Nanoparticles (Au@Pt NPs), and calculated the quantitative contribution of the ratio of the photothermal and photoelectrocatalysis effects towards the catalytic activity. The photothermal effect on the nanoparticle surface after illumination is detected by SERS. The photoelectrocatalytic effect generated from SPR is proved by SERS with a probe molecule of p-aminothiophenol (PATP).