Electrocatalytic Activity Research Articles

Ir Doping Modulates the Electronic Structure of Flower-Shaped Phosphides for Water Oxidation.

Electrolysis of water to produce hydrogen is an efficient, clean, and environmentally friendly hydrogen production method with unlimited development prospects. However, its overall efficiency is hampered by the slow oxygen evolution reaction (OER) with complex electron transfer processes. Therefore, designing efficient and low-cost OER catalysts is the key to solving this problem. In this paper, Ir-doped Co2P/Fe2P (abbreviated as Ir-CoFeP/NF) was grown on nickel foam through the strategies of low amount noble-metal doping and mild phosphating. Phosphide derived from a floral metal-organic framework (MOF) exhibits regular three-dimensional (3D) morphology and large active area, avoiding the stacking of active sites. The addition of Ir can effectively adjust the electronic structure, change the position of the d-band center, and increase active sites, thus enhancing the catalytic activity. Hence, the optimized catalyst exhibits unexpected electrocatalytic OER activity with an ideal overpotential of 213 mV at 10 mA cm-2, as well as a low Tafel slope of 40.63 mV dec-1. Coupling with Pt/C for overall water splitting (OWS), the entire device only needs an ultralow cell voltage of 1.50 V to achieve a current density of 10 mA cm-2. Besides, the OWS can be maintained for more than 70 h. This study demonstrates the superiority of Ir-doped phosphide in accelerating water oxidation.

ZnS-zeolitic imidazolate framework nanostructure anchored on Ni nanowires as a bifunctional electrocatalyst for high-efficiency overall water splitting

The design and construction of stable and inexpensive bifunctional catalysts for the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) present a challenge in electrocatalytic water splitting. In this study, we utilized zeolitic imidazolate frameworks-8 (ZIF-8) as the precursor to fabricate ZnS-ZIF-8 via facile sulfidation processes. The ZnS-ZIF-8 nanostructures were anchored on the surface of the nickel nanowire (denoted as Ni NWs@ ZnS-ZIF-8 nanocomposite) and their catalytic activity for HER, OER, and overall water splitting were studied. The prepared Ni NWs@ ZnS-ZIF-8 revealed a low overpotentials value of 90 and 260 mV at 10 mA cm−2 for HER and OER in 1.0 M KOH solution, respectively. The alkaline electrolyzer assembled by Ni NWs@ ZnS-ZIF-8 provides a low cell voltage of 1.61 V at 10 mA cm−2 current density to boost the overall water splitting and robust stability for 15 h. The superior electrocatalytic activity of Ni NWs@ ZnS-ZIF-8 is owing to the facile and effective electron transport of Ni NWs, accessible active sites of ZnS-ZIF-8, and as well as the synergistic effect of the nanocomposite structures. This finding presents a viable methodology for synthesizing a proficient noble-metal-free catalyst for energy conversion and storage.

Modulating NFO@N‐MWCNTs/CC Interfaces to Construct Multilevel Synergistic Sites (Ni/Fe‐O‐N‐C) for Multi‐Heavy Metal Ions Sensing

AbstractA hierarchical heterogeneous composite electrode of NiFe2O4@nitrogen‐doped multi‐walled carbon nanotubes/carbon cloth (NFO@N‐MWCNTs/CC) is prepared via a dip‐coating method, followed by a hydrothermal process. The flexible carbon cloth (CC) substrate provides robust support and the cross‐linked nitrogen‐doped multi‐walled carbon nanotubes (N‐MWCNTs) on the CC form a highly porous network with a large specific area that facilitates electron‐transfer. The stable support strengthens the framework and prevents pore structure disorder within the porous network, that could lead to the structural instability of the active sites. The decorated NiFe2O4 nanoparticles offer abundant active sites for enhanced electrocatalytic activity. Benefiting from the synergistic effect of the 3D hierarchical heterogeneous microstructure and multilevel bimetallic oxide active site (Ni/Fe‐O‐N‐C) constructs, the NFO@N‐MWCNTs/CC electrode achieves stable detection of multiple heavy metal ions (HMIs) with high reproducibility. The modified electrode allowed stable detection of multiple heavy metal ions with high reproducibility. The sensitivities of the electrode for Cd(II), Pb(II), Bi(III), and Hg(II) are 344.98, 441.02, 176.484, and 371.099 µA µm−1, respectively. The assay recoveries ranged from 95.3% to 106.8%, highlighting its practical applicability. This study provides innovative composites and theoretical insights to facilitate further advances in the simultaneous high‐performance detection of heavy metal ions.

Unveiling the Electrocatalytic Activity of Bifunctional Iron‐Niobium Double Perovskites for Overall Water Splitting: A‐Site Cation Influence

AbstractCapitalizing on the electrochemical conversion of water into hydrogen stands as a pivotal strategy in the global transition toward sustainable energy sources. This study investigates the influence of the A‐site cation type within A2FeNbO6 double perovskites (where A = Ca, Sr, or Ba) on their bifunctional electrocatalytic activities. The electrocatalytic performance is scrutinized in relation to charge transfer resistance, oxygen vacancy concentration, and metal‐oxygen covalency. Among the variants, Sr2FeNbO6 is distinguished as the optimal catalyst, achieving a current density of 10 mA cm⁻2 at overpotentials of 260 mV for the oxygen evolution reaction (OER) and 176 mV for the hydrogen evolution reaction (HER), thus matching the performance of leading metal oxide electrocatalysts. The study reveals pH‐dependent kinetics for Sr2FeNbO6, indicative of a lattice oxygen evolution mechanism for OER. An electrolyzer employing Sr2FeNbO6 electrodes for both the anode and cathode delivers a current density of 10 mA cm⁻2 at an efficient cell voltage of 1.76 V for complete alkaline water splitting, while also demonstrating exceptional stability. These insights advance the understanding of material optimization for electrocatalysis and position Sr2FeNbO6 as a viable catalyst for the sustainable production of hydrogen.

Iron phosphide nanoparticles anchored on 3D nitrogen-doped graphene as an efficient electrocatalysts for hydrogen evolution reaction in alkaline media

Electrocatalysts play a crucial role in hydrogen evolution reaction (HER), facilitating a clean and sustainable generation of hydrogen energy. To promote the HER process, it is imperative to employ highly efficient, stable, and cost-effective electrocatalysts. This research focuses on the design of iron phosphide nanoparticles anchored onto a porous three-dimensional nitrogen-doped graphene (FeP@3DNG). The porous framework of 3DNG serves a multifaceted purpose: it prevents the aggregation of FeP nanoparticles during phosphidation, safeguards the FeP electrocatalyst from oxidation during the HER, and simultaneously enhances electrical conductivity and stability. Notably, the FeP@3DNG nanocomposite demonstrated the efficient activity and highest HER activity with an overpotential of 76 mV to achieve 10 mA cm−2 and a small Tafel slope of 40.2 mV dec−1 as well as good long-term durability for 20 h in 1.0 M KOH solution. The high performance of the FeP@3DNG nanocomposite can be primarily corresponded to the synergistic effects of the highly active of FeP nanoparticles and advantages of porous three-dimensional graphene with excellent electrocatalytic activity, high specific surface area, and chemical stability, thus, resulting in the improvement the overall electrocatalytic activity.

Investigating the bifunctional electrocatalytic activity of nickel oxide/nitrogen-doped reduced graphene oxide nanocomposite for zinc-air battery application

Investigating the bifunctional electrocatalytic activity of nickel oxide/nitrogen-doped reduced graphene oxide nanocomposite for zinc-air battery application

Construction of PtAg‐on‐Au Heterostructured Nanoplates for Improved Electrocatalytic Activity of Formic Acid Oxidation

AbstractDirect formic acid fuel cells have attracted significant attention due to their low fuel crossover, high safety, and high theoretical power density among all proton‐exchange membrane fuel cells. Numerous efforts have been dedicated to studying formic acid oxidation, particularly in the fabrication of high‐performance electrocatalysts with economical utilization of Pt metal. In this work, we report a synthetic strategy to create PtAg dots supported on plate‐like Au nanoparticles and explore their applications in electrocatalytic formic acid oxidation. The highly dispersed nature of the catalytic Pt centers and the successful construction of PtAg−Au trimetallic interfaces makes the current nanostructure an ideal system to allow for a synergetic effect between Pt, Au, and Ag, leading to improved electrocatalysis. Compared with commercial Pt/C, our PtAg‐on‐Au heterogenous nanoplates exhibit superior mass activity, along with enhanced reaction kinetics and long‐term durability for FAOR in an acidic medium. Density functional theory (DFT) simulation results indicate that AgPtAu(111) exhibits a relatively high activity for HCOOH oxidation into CO2 among the various Au‐based catalysts. This work provides a viable strategy for constructing Pt‐based electrocatalysts with controlled Pt ensembles, offering insights into the development of fuel cell catalysts that make highly efficient use of costly noble metals.

Improving the Electrocatalytic Activity of a Core/Shell NiCo-ZIF@PBA Catalyst by Co-O-Fe Bridge Bonds for Water Oxidation.

In response to the limitations of slow reaction kinetics and elevated overpotentials in the OER, a novel core-shell structured electrocatalyst, termed NiCo-ZIF-67@Fe-Co-Ni-PBA or NiCo-ZIF@PBA, has been developed. This material demonstrates exceptional catalytic performance, exhibiting a minimal overpotential of approximately 188 mV at 10 mA cm-2, alongside a Tafel slope of 109 mV dec-1. Its robust stability in a 1 M KOH solution during the OER operations is noteworthy. Theoretical insights from DFT calculations reveal that a Co-O-Fe bridging configuration within NiCo-ZIF@PBA lowers the energy barrier for the reaction to 1.79 eV, a significant reduction from 2.67 eV observed with NiCo-ZIF-67. The improvement in electrochemical performance is primarily due to the emergence of Co3+ ions, which results from the efficient charge transfer occurring at the interface of the PBA and NiCo-ZIF core-shell structure. These findings suggest a promising strategy for designing advanced core-shell materials for electrocatalytic applications.

α-MnO2 with a cryptomelane structure for the non-enzymatic glucose electrooxidation in a neutral medium

A high demand for non-enzymatic glucose sensors and continuous glucose monitoring systems encourages the development of stable and active catalysts for the enzymeless anodic oxidation of glucose in the neutral medium. In regard to this reaction, we analyze the prospects of alpha manganese dioxide with a cryptomelane structure synthesized via an aqueous chemical route. To provide various specific surface area, the hydrated α-MnO2 oxide is annealed in a wide temperature range from 60 to 700 °C. Furthermore, we investigate the influence of the oxide annealing temperature on the amount of crystal water, chemical composition, morphology, electrochemical recharging behavior, electrocatalytic activity and stability in the glucose oxidation carried out in an isotonic NaCl-based phosphate-buffered saline (pH 7.40). To solidly determine potentials of the irreversible cathodic dissolution of α-MnO2 as well as O2/Cl2 evolution on α-MnO2, a rotating ring-disk electrode is applied. For the most active α-MnO2 sample with the 100 μg cm−2geo loading the glucose oxidation current of ca. 40 μA cm−2geo after 1 h at +0.8 V (SCE) for 7 mM of glucose is achieved. The linear concentration dependence in a physiological glucose range (1–30 mM) with the sensitivity of ca. 17.8 μA mM−0.5 cm−2geo at 25 °C is observed. Finally, glucose selectivity of α-MnO2 in relation to fructose, galactose, xylose, ribose, urea, lactic acid, acetone, ascorbic acid and paracetamol is revealed.

Computational screening of Group VⅢ@C5N4 single-atom electrocatalysts for overall water splitting

Single-atom catalysts (SACs) have great potential for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) since their high atomic utilization and strong metal–support interactions. Herein, we develop TM@C5N4 (TM = Fe, Co, Ni, Ru, Rh, Pd, Os, Ir and Pt) catalysts via embedding Group VⅢ TM in holey C5N4 substrate and further evaluate their electrocatalytic activity using density functional theory (DFT) calculations. Systematical studies indicate that Fe@C5N4, Pd@C5N4 and Ir@C5N4 catalysts all exhibit excellent HER performance, which mainly because of their small ΔGH* values of 0.101 eV, -0.114 eV and 0.070 eV, respectively. In parallel, Rh@C5N4 and Ir@C5N4 possess high OER activity along with low overpotential of 0.50 V, which is superior to the commercial IrO2 catalyst (0.56 V). Obviously, Ir@C5N4 could be utilized as bifunctional electrocatalysts both HER and OER in water splitting. Furthermore, we analyze their correlative catalytic mechanisms using the molecular orbitals. Besides, biaxial strain modulation could effectively regulate the catalytic activity of HER and OER. Particularly, 2 % biaxial tensile strain could bring Ir@C5N4 superb HER/OER catalytic performance. Finally, we anticipate that this strain engineering would provide a new perspective for developing high-performance SACs for water splitting.

Novel design of hollow carbon nanocage modified with nanotubes as a bifunctional electrocatalyst for high performance Zn–air batteries

Microcavities play a crucial role as microreactors in the transport of molecular/ionic guests and the exposure of active sites, thus significantly influencing the electrocatalytic performance. This study prepares Co/N-codoped hollow carbon (HT-CoN/C) with surface-distributed carbon nanotubes by pyrolysis of PDA-coated Zn/Co bimetallic ZIF (BM-ZIF@PDA). Benefiting from the hierarchical porous structure, high specific surface area (307.17 m2 g−1) and abundant Co clusters, the HT-CoN/C exhibits remarkable bifunctional oxygen electrocatalytic activity with an overpotential of the ORR/OER processes (ΔE = 0.703 V). The density functional theory (DFT) calculations also verify that the configuration of C-coated N-coordinated Co clusters (Co4-Nx) affect the electrocatalytic activity of ORR and OER, illustrating the source of the excellent oxygen electrocatalytic activity of HT-CoN/C. The aqueous rechargeable zinc-air battery (RZAB) using HT-CoN/C as the air electrode is characterized by a superior peak power density (175 mW cm−2), a prolonged cycle life (1230 cycles/410 h at 5.0 mA cm−2) and a high open-circuit voltage (1.47 V). Meanwhile, the flexible solid-state RZAB assembled by the HT-CoN/C also exhibits a higher peak power density (117 mW cm−2) and an excellent bending performance. This work is extremely valuable for the design and synthesis of Co/N co-doped carbon electrocatalysts.

Zirconium-doped lead dioxide anodes prepared by sol-gel method for ampicillin removal from simulated pharmaceutical polluted wastewater.

New anodes consisting of zirconium-doped PbO2 coating, growth on titanium dioxide interlayer, were deposited on titanium substrates using spin coating method and have been tested for the removal of ampicillin, a β-lactam antibiotic, from water. Morphological, structural, and electrochemical properties of the prepared coatings were characterized by scanning electron microscopy (SEM), atomic force microscope (AFM), X-ray diffraction (XRD), and electrochemical impendence spectroscopy (EIS). Results showed that the incorporation of zirconium dopant had a noticeable modification in the morphology of anodes. An increase in the surface roughness and the specific active area were observed with Ti/TiO2/PbO2- 10% Zr electrode compared to other anodes. The electrochemical measurements indicated that the anode doped with 10% Zr showed a more protective coating performance than the undoped and 20% Zr-doped PbO2 electrodes. The experiments on ampicillin degradation revealed that doped lead dioxide anodes have excellent electrocatalytic activity. The major byproduct generated during anodic oxidation treatment has been identified as ampicilloic acid by liquid chromatography-mass spectroscopy (LC-MS) analysis. Results demonstrated that Ti/TiO2/PbO2- 10% Zr anode presents the best removal rate of ampicillin with a minimum intermediate amount, which leads to conclude that 10% is the optimum percentage of zirconium dopant for antibiotic wastewater treatment.

Glassy Carbon Electrodes Modified with Ru Nanoparticles Loaded in B-Doped Imidazolium Porous Organic Polymers for Hydrogen Evolution Reaction.

Porous organic polymers (POPs) are a type of porous material composed of organic structural units connected by covalent bonds and POPs have been used as efficient electrocatalysts for hydrogen evolution reaction (HER). Herein, glassy carbon electrode (GCE) is chemically modified by B-doped imidazolium-based porous organic polymers loaded with Ru nanoparticles on the GCE surface. The incorporation of B in the POPs regulates the electronic structure of electrocatalysts to enhance their inherent electrocatalytic activity for HER. The optimized modified electrode GCE-Ru/PIM-Br2 exhibits a low overpotential of 271 mV at a current density of 10 mA cm-2 with a small Tafel slope (80 mV dec-1) in acidic solutions, and shows long-term stability for up to 22 h. This work presents a strategy to develop B-doped porous electrodes with loaded metal nanoparticles to strengthen the catalytic performance of electrocatalysts.

Nitrogen-doped carbon nanosheet confined PtNi alloy for efficient acidic electrocatalytic hydrogen evolution reaction

Low intrinsic electrocatalytic activity and inferior conductivity limit the application of Ni/NC in acidic electrocatalytic hydrogen evolution reaction (HER). Herein, we prepared nitrogen-doped carbon nanosheet confined PtNi alloy electrocatalysts (PtNi/NC-10) using PtCl62− electrostatic adsorption coupling melamine pyrolysis nitriding strategy. PtNi alloying was confirmed by the crystallinity decrease and lattice expansion of Ni/NC. The alloying and confinement effect of Metal-Organic Frameworks (MOFs) suppresses the oxidation and agglomeration of metal nanoparticles during pyrolysis, thus significantly reducing particle size, increasing specific surface area, and promoting the exposure of active sites. The strong electronic interaction between Pt and Ni optimizeds the surface charge distribution, enhancing the adsorption of H species on electron-rich Pt sites, thereby improving reaction kinetics. In addition, PtNi alloying improves the conductivity of the material, accelerating charge transfer and proton transport. Consequently, the prepared PtNi/NC-10 exhibits superior HER performance than Ni/NC in 0.5 M H2SO4 solution, even comparable to commercial 20 wt% Pt/C, with the overpotentials of 35 mV at 0.01 A cm−2. Furthermore, the electrocatalysts assembled PtNi/NC-10-CP‖RuO2-TFF proton exchange membrane (PEM) electrolyzer only requires 2.32 V cell voltage to achieve 1 A cm−2, presenting practical application prospects. Our work provides a novel idea for designing efficient and stable MOFs confined to alloy-based HER electrocatalysts.

α-Bi2Mo3O12: A Dual-Functional Material for Electrocatalytic Water Splitting and Supercapacitor Applications.

This study explores the functionality of α-Bi2Mo3O12 (BMO) as an electrocatalyst for water splitting and its suitability for supercapacitor applications. BMO was synthesized by the solvothermal method and characterized in pre-calcination [BMO (BC)], post-calcination [BMO (AC)], and base-etched forms [BMO (BE)]. Structural analysis confirmed the formation of α-Bi2Mo3O12 with well-defined crystallographic planes. Electrochemical analysis revealed that BMO (AC) exhibited the lowest overpotential for hydrogen evolution reactions (HER) and BMO (BC) exhibited the lowest overpotential for oxygen evolution reactions (OER), indicating its superior electrocatalytic activity. The Tafel slope and electrochemical impedance spectroscopy results confirmed the superior kinetics and charge transfer properties of BMO material. Furthermore, BMO samples demonstrated excellent stability during prolonged chronoamperometry (CA) testing for 12 h. For supercapacitor performances, the BMO (BE) exhibits a superior specific capacitance value of 398 F/g at 2.0 A/g. Thus, the BMO material delivers prominent electrocatalytic activity as well as supercapacitor performance. Overall, this study demonstrates the potentiality of α-Bi2Mo3O12 in different forms as a dual-functional material for efficient energy storage and conversion.

A Revised High‐Throughput Screening Model on Oxygen Reduction Reaction Over Dual Atom Catalysts Based on the Axial Pre‐Adsorption and O2 Adsorption

AbstractDual‐atom catalysts (DACs) often exhibit superior electrocatalytic activity, due to their versatile combinations and synergistic effects. However, the neglect of both dynamic axial adsorption of the active site upon working potential and the reactant adsorption as a rate‐determining step hinders the establishment of an accurate high‐throughput screening strategy. Here, the oxygen reduction reaction (ORR) of 42 kinds of 3d–3d metal DACs by density functional theory (DFT) calculations are systematiclly investigated and demonstrated that the ORR kinetics can be limited by O2* adsorption besides the proton–electron transfer step and the active center of DACs may be reconstructed by axial pre‐adsorption of intermediates under working potential. Therefore, the ORR volcano plot is proposed by using both the O2* and OH* adsorption as activity descriptors. Then, a high‐throughput screening method is constructed and 38 promising ORR DACs are screened out from 267 DACs containing 3d, 4d, or 5d metals. Importantly, the previously unexplored MnCoN6 DAC is also experimentally synthesized, and exhibits ultrahigh ORR activity outperforming Pt/C, perfectly matching with theoretical prediction. In short, this work not only proposes a volcano plot‐based high‐throughput screening method but also provides a proof‐of‐concept of experimental verification of theoretical prediction to heuristically design electrocatalysts for other reactions.

Magneto-electrochemical water splitting performance of graphene oxide/nickel aluminum-layered double hydroxide nanocomposites

Designing efficient, cheap catalysts for oxygen production is very important for water electrolysis and green hydrogen production. Here, synthesis and electrocatalytic performance of graphene oxide (GO)/nickel-aluminum layered double hydroxide (NiAl-LDH) composites were investigated for water-splitting applications. The composition, microstructure, and morphology of the nanocomposites were confirmed by X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FT-IR), and field emission scanning electron microscopy (FE-SEM), and their water oxidation performance was examined in 0.1 M potassium hydroxide solution in the presence and absence of magnetic field. The results show that optimized GO/NiAl-LDH nanocomposite (GO-1 %/NiAl-LDH) exhibits the lowest overpotential compared with other prepared nanocomposites. This performance demonstrates comparable electroactivity to well-developed electrocatalysts like the perovskite-based electrodes, it also shows an improved electrocatalytic activity compared to NiAl-LDHs due to the presence of graphene oxide in the composite. We interpreted this significant performance to improve electron transform and high active site at the synthesized GO/NiAl-LDH composites. The best electrocatalytic activity with an overpotential of 443 and 473 mV at the current density 10 mA.cm−2 were evidenced for GO-1 %/NiAl-LDH nanocomposite in the presence and absence of external magnetic field, respectively. Furthermore, the tafel slope were reported about 54 and 162 mV.dec−1 in the presence and absence of magnetic field, respectively. This improved water oxidation can be attributed to the magneto-hydrodynamic effect and the increased number of metal sites on LDHs under the magnetic field.

Tailoring of Time for Hydrothermal Synthesis of 2D MoSe2 with Enhanced Adsorption and Electro‐Catalytic Efficiency for Applications in Self‐Cleaning and Hydrogen Energy Generation

AbstractMolybdenum diselenide (MoSe2), a 2D layered transition metal dichalcogenide, has garnered significant scientific research interest for its catalytic and electrocatalytic activities. Here, a straightforward hydrothermal procedure is used to synthesize MoSe2 nanosheets (NSs) and focus on their adsorption capabilities and hydrogen evolution reaction (HER) activity. The MoSe2 NSs which are synthesized by 12 h of hydrothermal treatment found to exhibit the highest adsorption capacity of 91.67 mg g−1. The kinetics of the adsorption process have been found to follow the pseudo‐second‐order model, signifying chemisorption and multilayer adsorption as described by the Freundlich isotherm. The thermodynamic analysis further suggests that the adsorption proceeds by endothermic and spontaneous mechanisms. The self‐cleaning property of the adsorbent is demonstrated by degrading the dye on the adsorbent‐coated cotton fabric. The sample created using a 12 h hydrothermal method has been shown to have a minimal Tafel slope of 58 mV dec−1. It also shows excellent HER activity at low over‐potential and possesses long‐term durability. The dual functionality of MoSe2 NSs in both adsorption and electrocatalytic activity highlights their potential for application in environmental remediation and renewable energy production.

The effect of glass sealing stabilization on LSM–YSZ cathode poisoning and oxygen reduction reaction processes in solid oxide fuel cell

AbstractThe perovskite structure and electrochemical activity of (La0.80Sr0.20)0.95MnO3−x–(Y2O3)0.08(ZrO2)0.92 (LSM–YSZ) composite cathode can be significantly affected by volatile boron species originated from sealing glass–ceramics. Herein, we investigate the impact of doping the varying Er2O3 content (ranging from 0 to 4%) into an aluminoborosilicate glass to mitigate boron volatilization, its interaction with the LSM–YSZ cathode and consequent effects on its electrochemical performance. The results reveal that the volatility of boron species can be significantly suppressed by introducing Er oxide into the glass network by enhancing the conversion of [BO3] to [BO4] units, thereby increasing the binding energy of boron and strengthening of the glass structure. Moreover, the electrocatalytic performance for the O2 reduction reaction on the LSM–YSZ/8YSZ/LSM–YSZ symmetric cells is studied under open‐circuit conditions in the presence and absence of glass sealants. The analyses utilizing electrochemical impedance spectroscopy (EIS) and distribution of the relaxation times (DRT) analysis indicate that the electrocatalytic performance of LSM–YSZ cathodes can be enhanced in the presence of glass with 4% Er2O3 (GE4). This enhancement in the electrocatalytic activity of the LSM–YSZ electrode for the oxygen reduction reaction (ORR) is attributed to formation of the thin layer on the electrode surface, leading to a notable reduction in the polarization resistance (Rp) from 0.81 Ω cm2 in the glass absence to 0.45 Ω cm2 in the presence of GE4. However, DRT analysis demonstrates that the prolonged exposure of the cathode to GE4 causes a deterioration in cell performance primarily due to the blocking the cathode active sites, which impedes dominant cathode processes of oxygen dissociative adsorption/desorption and charge transfer and consequently reducing kinetics of the ORR.

Theory-driven design of local spin-state modulation at atomically dispersed iron sites for enhanced CO2 electroreduction

Herein, density functional theory (DFT) was used to guide the systematic design of highly efficient single-atom electrocatalysts to improve the kinetics of the CO2 reduction reaction (CO2RR). We present a novel class of catalysts that exhibit magnetic-proximity-induced exchange splitting (spin polarization). The design of these catalysts involved the precise modulation of d-shell energy levels at metallic sites and the subsequent alteration of the atomic/molecular orbitals of the adsorbed intermediates. To validate the effectiveness of our design strategy, we introduced neighboring nitrogen (N) doping near the Fe-N4 coordination environment, demonstrating the successful manipulation of the local spin state of the active sites. The results of the theoretical calculations align with the experimental results, with remarkable selectivity exceeding 90 % at low potentials (<-0.5 V vs. RHE) and sustained electrocatalytic activity for over 24 h. In situ characterization further revealed that a modulated local spin state led to a decrease in the occupation of the Fe 3d spin-down electronic states below the Fermi level. Concurrently, electrons migrated to the frontier antibonding orbitals of *COOH. This dual effect resulted in a lower reaction energy (ΔG), representing a thermodynamic benefit, and accelerated proton transfer to *COOH, representing a kinetic benefit, collectively enhancing the electrocatalytic process.