Atomic Magnetic Heating Effect Enhanced Hydrogen Evolution Reaction of Gd@MoS2 Single-Atom Catalysts

Atomic heating on single atoms (SAs) to maximize the catalytic efficiency of each active site would be a fascinating solution to break the bottleneck for the performance improvement of single-atom catalysts (SACs) but highly challenging task. Here, based on the Gd@MoS₂ SACs synthesized by a facile laser molecular beam epitaxy method, high-frequency alternating magnetic field (AMF) technology is employed to induce atomic magnetic heating on Gd SAs that is meanwhile demonstrated to be the catalytic active center. Significant improvement in catalytic kinetics under AMF excitation (3.9 mT) is achieved, yielding a remarkable enhancement of hydrogen evolution reaction magnetothermal-current by ≈924%. Through theoretical calculations and spin-related electrochemical experiments, such promotion in catalyst activity can be attributed to spin flip (or canting) in Gd SAs leading to the atomic magnetic heating effect on catalytic active center. Together with the embodied high stability, the implement of AMF to the SAs field is demonstrated in this work, and the precisely atomic magnetic heating on specific SAs offers unprecedented thinking for further improvement of SACs performance in the future.     

Magnetic Heating Amorphous NiFe Hydroxide Nanosheets Encapsulated Ni Nanoparticles@Wood Carbon to Boost Oxygen Evolution Reaction Activity

The oxygen evolution reaction (OER) has significant effects on the water-splitting process and rechargeable metal-air batteries; however, the sluggish reaction kinetics caused by the four-electron transfer process for transition metal catalysts hinder large-scale commercialization in highly efficient electrochemical energy conversion devices. Herein, a magnetic heating-assisted enhancement design for low-cost carbonized wood with high OER activity is proposed, in which Ni nanoparticles are encapsulated in amorphous NiFe hydroxide nanosheets (a-NiFe@Ni-CW) via direct calcination and electroplating. The introduction of amorphous NiFe hydroxide nanosheets optimizes the electronic structure of a-NiFe@Ni-CW, accelerating electron transfer and reducing the energy barrier in the OER. More importantly, the Ni nanoparticles located on carbonized wood can function as magnetic heating centers under the effect of an alternating current (AC) magnetic field, further promoting the adsorption of reaction intermediates. Consequently, a-NiFe@Ni-CW demonstrated an overpotential of 268 mV at 100 mA cm⁻² for the OER under an AC magnetic field, which is superior to that of most reported transition metal catalysts. Starting with sustainable and abundant wood, this work provides a reference for highly effective and low-cost electrocatalyst design with the assistance of a magnetic field.     

Electrochemical Oxidation Encapsulated Ru Clusters Enable Robust Durability for Efficient Oxygen Evolution (Small 29/2023)

Electrochemical oxidization and thermodynamic instability agglomeration are a primary challenge in triggering metal-support interactions (MSIs) by immobilizing metal atoms on a carrier to achieve efficient oxygen evolution reactions (OER). Herein, Ru clusters anchored to the VS₂ surface and the VS₂ nanosheets embedded vertically in carbon cloth (Ru-VS₂@CC) are deliberately designed to realize high reactivity and exceptional durability. In situ Raman spectroscopy reveals that the Ru clusters are preferentially electro-oxidized to form RuO₂ chainmail, both affording sufficient catalytic sites and protecting the internal Ru core with VS₂ substrates for consistent MSIs. Theoretical calculations elucidate that electrons across the Ru/VS₂ interface aggregate toward the electro-oxidized Ru clusters, while the electronic coupling of Ru 3p and O 2p orbitals boosts a positive shift in the Fermi energy level of Ru, optimizing the adsorption capacity of the intermediates and diminishing the migration barriers of the rate-determining steps. Therefore, the Ru-VS₂@CC catalyst demonstrated ultra-low overpotentials of 245 mV at 50 mA cm⁻², while the zinc–air battery maintained a narrow gap (0.62 V) after 470 h of reversible operation. This work has transformed the corrupt into the miraculous and paved a new way for the development of efficient electrocatalysts.     

Efficient Ternary Mn-Based Spinel Oxide with Multiple Active Sites for Oxygen Evolution Reaction Discovered via High-Throughput Screening Methods (Small 2/2023)

The discovery of more efficient and stable catalysts for oxygen evolution reaction (OER) is vital in improving the efficiency of renewable energy generation devices. Given the large numbers of possible binary and ternary metal oxide OER catalysts, high-throughput methods are necessary to accelerate the rate of discovery. Herein, Mn-based spinel oxide, Fe₁₀Co₄₀Mn₅₀O, is identified for the first time using high-throughput methods demonstrating remarkable catalytic activity (overpotential of 310 mV on fluorine-doped tin oxide (FTO) substrate and 237 mV on Ni foam at 10 mA cm⁻²). Using a combination of soft X-ray absorption spectroscopy and electrochemical measurements, the high catalytic activity is attributed to 1) the formation of multiple active sites in different geometric sites, tetrahedral and octahedral sites; and 2) the formation of active oxyhydroxide phase due to the strong interaction of Co²⁺ and Fe³⁺. Structural and surface characterizations after OER show preservation of Fe₁₀Co₄₀Mn₅₀O surface structure highlighting its durability against irreversible redox damage on the catalytic surface. This work demonstrates the use of a high-throughput approach for the rapid identification of a new catalyst, provides a deeper understanding of catalyst design, and addresses the urgent need for a better and stable catalyst to target greener fuel.     

External Fields Assisted Highly Efficient Oxygen Evolution Reaction of Confined 1T-VSe2 Ferromagnetic Nanoparticles (Small 38/2023)

As a clean and effective approach, the introduction of external magnetic fields to improve the performance of catalysts has attracted extensive attention. Owing to its room-temperature ferromagnetism, chemical stability, and earth abundance, VSe₂ is expected to be a promising and cost-effective ferromagnetic electrocatalyst for the accomplishment of high-efficient spin-related OER kinetics. In this work, a facile pulsed laser deposition (PLD) method combined with rapid thermal annealing (RTA) treatment is used to successfully confine monodispersed 1T-VSe₂ nanoparticles in amorphous carbon matrix. As expected, with external magnetic fields of 800 mT stimulation, the confined 1T-VSe₂ nanoparticles exhibit highly efficient oxygen evolution reaction (OER) catalytic activity with an overpotential of 228 mV for 10 mA cm⁻² and remarkable durability without deactivation after >100 h OER operation. The experimental results together with theoretical calculations illustrate that magnetic fields can facilitate the surface charge transfer dynamics of 1T-VSe₂, and modify the adsorption-free energy of *OOH, thus finally improving the intrinsic activity of the catalysts. This work realizes the application of ferromagnetic VSe₂ electrocatalyst in highly efficient spin-dependent OER kinetics, which is expected to promote the application of transition metal chalcogenides (TMCs) in external magnetic field-assisted electrocatalysis.     

Electrochemical Etching Switches Electrocatalytic Oxygen Evolution Pathway of IrOx/Y2O3 from Adsorbate Evolution Mechanism to Lattice-Oxygen-Mediated Mechanism

Oxygen evolution reaction (OER) plays key roles in electrochemical energy conversion devices. Recent advances have demonstrated that OER catalysts through lattice oxygen-mediated mechanism (LOM) can bypass the scaling relation-induced limitations on those catalysts through adsorbate evolution mechanism (AEM). Among various catalysts, IrO_x, the most promising OER catalyst, suffers from low activities for its AEM pathway. Here, it is demonstrated that a pre-electrochemical acidic etching treatments on the hybrids of IrO_x and Y₂O₃ (IrO_x/Y₂O₃) switch the AEM-dominated OER pathway to LOM-dominated one in alkali electrolyte, delivering a high performance with a low overpotential of 223 mV at 10 mA cm⁻² and a long-term stability. Mechanism investigations suggest that the pre-electrochemical etching treatments create more oxygen vacancies in catalysts due to the dissolution of yttrium and then provide highly active surface lattice oxygen for participating OER, thereby enabling the LOM-dominated pathway and resulting in a significantly increased OER activity in basic electrolyte.     

Fabrication of Hollow CoP/TiOx Heterostructures for Enhanced Oxygen Evolution Reaction

Transition‐metal phosphides have flourished as promising candidates for oxygen evolution reaction (OER) electrocatalysts. Herein, it is demonstrated that the electrocatalytic OER performance of CoP can be greatly improved by constructing a hybrid CoP/TiO_x heterostructure. The CoP/TiO_x heterostructure is fabricated using metal–organic framework nanocrystals as templates, which leads to unique hollow structures and uniformly distributed CoP nanoparticles on TiO_x. The strong interactions between CoP and TiO_x in the CoP/TiO_x heterostructure and the conductive nature of TiO_x with Ti³⁺ sites endow the CoP–TiO_x hybrid material with high OER activity comparable to the state‐of‐the‐art IrO₂ or RuO₂ OER electrocatalysts. In combination with theoretical calculations, this work reveals that the formation of CoP/TiO_x heterostructure can generate a pathway for facile electron transport and optimize the water adsorption energy, thus promoting the OER electrocatalysis.     

Engineering NiO/NiFe LDH Intersection to Bypass Scaling Relationship for Oxygen Evolution Reaction via Dynamic Tridimensional Adsorption of Intermediates

Oxygen evolution reaction (OER) is a pivotal reaction in many technologies for renewable energy, such as water splitting, metal–air batteries, and regenerative fuel cells. However, this reaction is known to be kinetically sluggish and proceeds at rather high overpotential due to the universal scaling relationship, namely, the adsorption energies of intermediates are linearly correlated and cannot be optimized simultaneously. Several approaches have been proposed to break the scaling relationship by introducing additional active sites; however, positive experimental results are still absent. Herein, a different solution is suggested on the basis of dynamic tridimensional adsorption of the OER intermediates at NiO/NiFe layered double hydroxide intersection, by which the adsorption energy of each intermediate can be adjusted independently, so as to bypass the scaling relationship and achieve high catalytic performance. Experimentally, the OER overpotential is reduced to ≈205 mV at current density of 30 mA cm^?2, which represents the best performance achieved by state‐of‐the‐art OER catalysts.     

Tuning Surface Electronic Configuration of NiFe LDHs Nanosheets by Introducing Cation Vacancies (Fe or Ni) as Highly Efficient Electrocatalysts for Oxygen Evolution Reaction

Intrinsically inferior electrocatalytic activity of NiFe layered double hydroxides (LDHs) nanosheets is considered as a limiting factor to inhibit the electrocatalytic properties for oxygen evolution reaction (OER). Proper defect engineering to tune the surface electronic configuration of electrocatalysts may significantly improve the intrinsic activity. In this work, the selective formation of cation vacancies in NiFe LDHs nanosheets is successfully realized. The as‐synthesized NiFe LDHs‐V_Fe and NiFe LDHs‐V_Ni electrocatalysts show excellent activity for OER, mainly attributed to the introduction of rich iron or nickel vacancies in NiFe LDHs nanosheets, which efficiently tune the surface electronic structure increasing the adsorbing capacity of OER intermediates. Density functional theory (DFT) computational results also further indicate that the OER catalytic performance of NiFe LDHs can be pronouncedly improved by introducing Fe or Ni vacancies.     

Super-Hydrophilic Microporous Ni(OH)x/Ni3S2 Heterostructure Electrocatalyst for Large-Current-Density Hydrogen Evolution

Exploiting active and stable non-precious metal electrocatalysts for alkaline hydrogen evolution reaction (HER) at large current density plays a key role in realizing large-scale industrial hydrogen generation. Herein, a self-supported microporous Ni(OH)x/Ni₃S₂ heterostructure electrocatalyst on nickel foam (Ni(OH)x/Ni₃S₂/NF) that possesses super-hydrophilic property through an electrochemical process is rationally designed and fabricated. Benefiting from the super-hydrophilic property, microporous feature, and self-supported structure, the electrocatalyst exhibits an exceptional HER performance at large current density in 1.0 M KOH, only requiring low overpotential of 126, 193, and 238 mV to reach a current density of 100, 500, and 1000 mA cm⁻², respectively, and displaying a long-term durability up to 1000 h, which is among the state-of-the-art non-precious metal electrocatalysts. Combining hard X-rays absorption spectroscopy and first-principles calculation, it also reveals that the strong electronic coupling at the interface of the heterostructure facilitates the dissociation of H₂O molecular, accelerating the HER kinetics in alkaline electrolyte. This work sheds a light on developing advanced non-precious metal electrocatalysts for industrial hydrogen production by means of constructing a super-hydrophilic microporous heterostructure.     

Promoting Oxygen Evolution Reaction of Co‐Based Catalysts (Co3O4, CoS,CoP, and CoN) through Photothermal Effect

The increase of reaction temperature of electrocatalysts is regarded as an efficient method to improve the oxygen evolution reaction (OER) activity. Herein, it is reported that the electrocatalytic performance of dual functional (i.e., electrocatalytic and photothermal functions) Co₃O₄ can be dramatically improved via its photothermal effect. The operating temperature of the Co₃O₄ electrode is elevated in situ under near infrared (NIR) light irradiation, resulting in enhanced oxygen evolution activity due to its accelerated electrical conductivity, reaction kinetics, and desorption rate of O₂ bubbles from the electrode. In addition, photothermal effect can also enhance the electrocatalytic reaction rates of metal‐doped Co₃O₄ electrodes, indicating that it is able to significantly improve the OER activities of electrodes together with other modification strategies. With the assistance of the photothermal effect, the obtained Ni‐doped Co₃O₄ catalyst requires an extremely low overpotential of 208 mV to achieve a benchmark of 10 mA cm^?2 with a small Tafel slope, superior to most reported Co‐based catalysts. Significantly, the electrocatalytic performance of other electrodes with photothermal effect, such as CoN, CoP, and CoS, are also boosted under NIR light irradiation, indicating opportunities for implementing photothermal enhancement in electrocatalytic water splitting.