Fe Sites Research Articles

Noncollinear Magnetic Structures in the Chiral Antiperovskite β-Fe2SeO.

We present the magnetic properties of the chiral, polar, and possibly magnetoelectric antiperovskite β-Fe2SeO as derived from magnetization and specific-heat measurements as well as from powder neutron diffraction and Mössbauer experiments. Our macroscopic data unambiguously reveal two magnetic phase transitions at TN1 ≈ 103 K and TN2 ≈ 78 K, while Rietveld analysis of neutron powder diffraction data reveals a noncollinear antiferromagnetic structure featuring magnetic moments in the a-b plane of the trigonal structure and a ferromagnetic moment along c. The latter is allowed by symmetry between TN1 and TN2, weakly visible in the magnetization data yet unresolvable microscopically. While the intermediate phase can be expressed in the trigonal magnetic space group P31, the magnetic ground state is modulated by a propagation vector q = (1/2 1/2 0) resulting in triclinic symmetry and an even more complex low-temperature spin arrangement which is also reflected in the Mössbauer hyperfine patterns indicating additional splitting of Fe sites below TN2. The complex noncollinear spin arrangements suggest interesting magnetoelectric properties of this polar magnet.

Low-Spin Fe3+ Evoked by Multiple Defects with Optimal Intermediate Adsorption Attaining Unparalleled Performance in Water Oxidation.

Electrocatalytic water splitting is long constrained by the sluggish kinetics of anodic oxygen evolution reaction (OER), and rational spin-state manipulation holds great promise to break through this bottleneck. Low-spin Fe3+ (LS, t2g 5eg 0) species are identified as highly active sites for OER in theory, whereas it is still a formidable challenge to construct experimentally. Herein, a new strategy is demonstrated for the effective construction of LS Fe3+ in NiFe-layered double hydroxide (NiFe-LDH) by introducing multiple defects, which induce coordination unsaturation over Fe sites and thus enlarge their d orbital splitting energy. The as-obtained catalyst exhibits extraordinary OER performance with an ultra-low overpotential of 244 mV at the industrially required current density of 500 mA cm-2, which is 110 mV lower than that of the conventional NiFe-LDH with high-spin Fe3+ (HS, t2g 3eg 2) and superior to most previously reported NiFe-based catalysts. Comprehensive experimental and theoretical studies reveal that LS Fe3+ configuration effectively reduces the adsorption strength of the O* intermediate compared with that of the HS case, thereby altering the rate-determining step from (O* → OOH*) to (OH* → O*) of OER and lowering its reaction energy barrier. This work paves a new avenue for developing efficient spin-dependent electrocatalysts for OER and beyond.

Iron-Based Layered Perovskite Oxyfluoride Electrocatalyst for Oxygen Evolution: Insights from Crystal Facets with Heteroanionic Coordination.

Mixed-anion compounds have recently attracted attention as solid-state materials that exhibit properties unattainable with those of their single-anion counterparts. However, the use of mixed-anion compounds to control the morphology and engineer the crystal facets of electrocatalysts has been limited because their synthesis method is still immature. This study explored the electrocatalytic properties of a Pb-Fe oxyfluoride, Pb3Fe2O5F2, with a layered perovskite structure for oxygen evolution reaction (OER) and compared its properties in detail with those of a bulk-type cubic three-dimensional (3D) perovskite, PbFeO2F. A Pb3Fe2O5F2 electrode prepared with carbon nanotubes and a graphite sheet as a conductive support and a substrate, respectively, demonstrated better OER performance than a PbFeO2F electrode. The role of specific crystal facets of Pb3Fe2O5F2 in enhancing the OER activity was elucidated through electrochemical analysis. Density functional theory calculations indicated that the Pb3Fe2O5F2 (060) facet with Fe sites exhibited a lower theoretical overpotential for the OER, which was attributed to a moderately strong interaction between the active sites and the reaction intermediates; this interaction was reinforced by the strong electron-withdrawing behavior of fluoride ions. This finding offers new insights for developing efficient electrocatalysts based on oxyfluorides, leveraging the high electronegativity of fluorine to optimize the electronic states at active sites for the OER, without relying on precious metals.

Mn-Fe Dual-Metal Assemblages on Carbon-Coated Al2O3 Spheres for Catalytic Ozonation Oxidation: Structure, Performance, and Reaction Mechanism.

Catalysts with high catalytic activity and low production cost are important for industrial application of heterogeneous catalytic ozonation (HCO). In this study, we designed a carbon-coated aluminum oxide carrier (C-Al2O3) and reinforced it with Mn-Fe bimetal assemblages to prepare a high-performance catalyst Mn-Fe/C-Al2O3. The results showed that the carbon embedding significantly improved the abundance of surface oxygen functional groups, conductivity, and adsorption capacity of γ-Al2O3, while preserving its exceptional mechanical strength as a carrier. The prepared Mn-Fe/C-Al2O3 catalyst exhibited satisfactory catalytic ozonation activity and stability in the degradation of p-nitrophenol (PNP). Electron paramagnetic resonance (EPR) and quenching experiments reveal that radical ( ⋅ OH and ⋅ O2 ⋅ ) and nonradical oxidation (1O2) dominated the PNP degradation process. Theoretical calculations corroborated that the anchored atomic Fe and Mn sites regulated the local electronic structure of the catalyst. This modulation effectively promoted the activation of O3 molecules, resulting in the generation of atomic oxygen species (AOS) and reactive oxygen species (ROS). The economic analysis on Mn-Fe/C-Al2O3 revealed that it was a cost-competitive catalyst for HCO. This study not only deepens the understanding on the reaction mechanism of HCO with transition metal/carbon composite catalysts, also provides a high-performance and cost-competitive ozone catalyst for prospective application.

Revealing Active Sites and Reaction Pathways in Direct Oxidation of Methane over Fe-Containing CHA Zeolites Affected by the Al Arrangement.

Fe-containing zeolites are effective catalysts in converting the greenhouse gases CH4 and N2O into valuable chemicals. However, the activities of Fe-containing zeolites in methane conversion and N2O decomposition are frequently conflated, and the activities of different Fe species are still controversial. Herein, Fe-containing aluminosilicate CHA zeolites with Fe species at different spatial distances affected by the arrangement of framework Al atoms were synthesized in a one-pot manner in the presence or absence of Na. The arrangement of framework Al atoms was identified by 27Al and 29Si MAS NMR spectra and thermogravimetry-differential thermal analysis (TG-DTA) curves. Ultraviolet (UV)-vis, X-ray absorption spectroscopy (XAS), and NO adsorption fourier transform infrared spectroscopy (FTIR) spectra were adopted to analyze Fe speciation. The higher proportion of Fe species in the 6 MR of Fe-CHA zeolites in the presence of Na was confirmed by the NO adsorption FTIR spectrum. The activities of proximal and distant Fe sites in reactions including direct oxidation of methane to methanol, methanol to hydrocarbon, and N2O decomposition were compared at different temperatures to provide the corresponding active sites and reaction pathways. The distant, isolated Fe and isolated proton were more active in the direct oxidation of methane to methanol and tandem conversion of methanol to hydrocarbon reactions than the proximal, isolated Fe and paired protons, respectively. Additionally, proximal, isolated Fe sites afforded higher activity in N2O decomposition. These findings guide the design of highly active catalysts in methane oxidation, methanol to hydrocarbon, and N2O decomposition reactions, addressing energy and environmental concerns.

Iron-Induced Localized Oxide Path Mechanism Enables Efficient and Stable Water Oxidation.

The sluggish reaction kinetics of the anodic oxygen evolution reaction (OER) and the inadequate catalytic performance of non-noble metal-based electrocatalysts represent substantial barriers to the development of anion exchange membrane water electrolyzer (AEMWE). This study performed the synthesis of a three-dimensional (3D) nanoflower-like electrocatalyst (CFMO) via a simple one-step method. The substitution of Co with Fe in the structure induces a localized oxide path mechanism (LOPM), facilitating direct O-O radical coupling for enhanced O2 evolution. The optimized CFMO-2 electrocatalyst demonstrates superior OER performance, achieving an overpotential of 217 mV at 10 mA cm-2, alongside exceptional long-term stability with minimal degradation after 1000 h of operation in 1.0 M KOH. These properties surpass most of conventional noble metal-based electrocatalysts. Furthermore, the assembled AEMWE system, utilizing CFMO-2, operates with a cell voltage of 1.65 V to deliver 1.0 A cm-2. In situ characterizations reveal that, in addition to the traditional adsorbate evolution mechanism (AEM) at isolated Co sites, a new LOPM occurred around the Fe and Co bimetallic sites. First-principles calculations confirm the LOPM greatly reduced the energy barriers. This work highlights the potential of LOPM for improving the design of non-noble metal-based electrocatalysts and the development of AEMWE.

Iron‐Induced Localized Oxide Path Mechanism Enables Efficient and Stable Water Oxidation

The sluggish reaction kinetics of the anodic oxygen evolution reaction (OER) and the inadequate catalytic performance of non‐noble metal‐based electrocatalysts represent substantial barriers to the development of anion exchange membrane water electrolyzer (AEMWE). This study performed the synthesis of a three‐dimensional (3D) nanoflower‐like electrocatalyst (CFMO) via a simple one‐step method. The substitution of Co with Fe in the structure induces a localized oxide path mechanism (LOPM), facilitating direct O–O radical coupling for enhanced O2 evolution. The optimized CFMO‐2 electrocatalyst demonstrates superior OER performance, achieving an overpotential of 217 mV at 10 mA cm–2, alongside exceptional long‐term stability with minimal degradation after 1000 h of operation in 1.0 M KOH. These properties surpass most of conventional noble metal‐based electrocatalysts. Furthermore, the assembled AEMWE system, utilizing CFMO‐2, operates with a cell voltage of 1.65 V to deliver 1.0 A cm–2. In situ characterizations reveal that, in addition to the traditional adsorbate evolution mechanism (AEM) at isolated Co sites, a new LOPM occurred around the Fe and Co bimetallic sites. First‐principles calculations confirm the LOPM greatly reduced the energy barriers. This work highlights the potential of LOPM for improving the design of non‐noble metal‐based electrocatalysts and the development of AEMWE.

A Hypothesis on the Function of High‐Valent Fe in NiFe (Hydr)oxide in the Oxygen‐Evolution Reaction

This study investigated the dynamic changes in NiFe (hydr)oxide and identified the role of high‐valent Fe in the oxygen‐evolution reaction (OER) within alkaline media via in‐situ techniques. Several high‐valent Fe ions were found to remain considerably stable in the absence of potential in NiFe (hydr)oxide, even 96 hours after the OER. For Ni2+ hydroxide treated with 57Fe ions, where Fe sites are introduced onto the surface of Ni2+ hydroxide, no Fe4+ species were detected at the rate‐determining step (RDS). The findings of this study suggested that the oxidation of bulk Fe ions, similar to Ni ions, to high valent forms, is charge accumulation without a direct role in OER; these results offered a novel perspective on manipulating Fe states to optimize OER efficacy. The prevailing hypothesis suggested that trace amounts of high‐valent Fe ions, notably those on the surface, directly participate in OER.

A Hypothesis on the Function of High-Valent Fe in NiFe (Hydr)oxide in the Oxygen-Evolution Reaction.

This study investigated the dynamic changes in NiFe (hydr)oxide and identified the role of high-valent Fe in the oxygen-evolution reaction (OER) within alkaline media via in-situ techniques. Several high-valent Fe ions were found to remain considerably stable in the absence of potential in NiFe (hydr)oxide, even 96 hours after the OER. For Ni2+ hydroxide treated with 57Fe ions, where Fe sites are introduced onto the surface of Ni2+ hydroxide, no Fe4+ species were detected at the rate-determining step (RDS). The findings of this study suggested that the oxidation of bulk Fe ions, similar to Ni ions, to high valent forms, is charge accumulation without a direct role in OER; these results offered a novel perspective on manipulating Fe states to optimize OER efficacy. The prevailing hypothesis suggested that trace amounts of high-valent Fe ions, notably those on the surface, directly participate in OER.

Investigation of a Single Atom Iron Catalyst for the Electrocatalytic Reduction of Nitric Oxide to Hydroxylamine: A DFT Study.

Hydroxylamine, as an important reducing agent, disinfectant, foaming agent, and biocide, plays a role in both human life and industrial production. However, its synthesis is confronted with challenges, such as high pollution and large consumption. Here, we propose a coordination tailoring strategy to design 47 graphene-supported single iron atom catalysts (SACs), namely, Fe@CxZy (Z = B, N, O, P, and S), for the reduction of nitric oxide to hydroxylamine. Using density functional theory calculations, we demonstrated the great impact of the coordination environment on the stability, catalytic selectivity, and activity of the Fe site. We identified that the experimentally available Fe@N4 possesses an ultralow theoretical limiting potential of -0.32 V compared to that of other catalysts. A comprehensive investigation of the electronic properties elucidates the underlying active origin and reaction mechanism of the nitric oxide reduction reaction to hydroxylamine on Fe@N4. These results not only explain the catalytic origin of synthesized SACs for the NH2OH production but also offer theoretical guidance for further optimizing high-performance catalysts.

Regulating N-doped biochar with Fe-Mo heterojunctions as cathode in long-life zinc-air battery

Carbonaceous electrode loaded nano Mo2C-Fe3N@NCF was synthesized by solvothermal and pyrolysis from soybean straw for high-performance zinc-air batteries (ZABs). The empowered ZAB achieved 1.51 V open-circuit voltage, 88.40 mW cm−2 power density and over 1150 h cycle life. Density functional theory analysis indicates that charge transfer from Mo2C-Fe3N heterogeneous structure to N-doped biochar can significantly reduce the reaction barrier for oxygen reduction/evolution reactions, enhancing the adsorption of oxygen intermediates. Cellulose-derived carbon provides a large specific surface area, and N-doping enhances the conductivity of the resultant biochar, which both play a crucial role in the efficient loading of Fe and Mo active sites. This work inspires the design and application of interfacial engineering on low-cost biochar carriers.

Cr-doped NiFe sulfides nanoplate array: Highly efficient and robust bifunctional electrocatalyst for the overall water splitting and seawater electrolysis

To replace precious metals and reduce production costs for large-scale hydrogen production, developing stable, high-performance transition metal electrocatalysts that can be used in a wide range of environments is desirable yet challenging. Herein, a self-supported hybrid catalyst (NiFeCrSx/NF) with high electrocatalytic activity was designed and constructed using conductive nickel foam as a substrate via manipulation of the cation doping ratio of transition metal compounds. Due to the strong coupling synergy between the metal sulfides NiS2, Fe9S11, and Cr2S3, as well as their interaction with the conductive nickel foam (NF), the energy barrier for catalytic reactions is reduced, and the charge transfer rate is enhanced. This significantly improves the hydrogen evolution reaction (HER) performance of NiFeCrSx/NF, achieving a current density of 10 mA cm−2 with an overpotential of just 66 mV. Furthermore, doping with chromium generates different valence states of Cr during the catalytic process, which can synergize with the high-valent Fe and Ni, promoting the formation of oxygen vacancies and enriching the active sites for the oxygen evolution reaction (OER). Consequently, at a current density of 10 mA cm−2 in 1.0 M KOH, the overpotential for OER is only 223 mV for NiFeCrSx/NF. Additionally, the in situ grown of self-supporting nanoflower structure on NiFe-LDH not only provides a large catalytic surface area but also facilitates electrolyte penetration during the catalytic process, endowing NiFeCrSx/NF with high long-term stability. When used as a bifunctional catalyst for overall water splitting, the NiFeCrSx/NF||NiFeCrSx/NF electrolyzer requires only 1.29 V to deliver a current density of 10 mA cm−2. Simultaneously, Cr doping protects the Fe sites by maintaining stable valence states, ensuring high performance and stability of NiFeCrSx/NF, even when it is utilized for seawater splitting. This strategy offers novel concepts for creating catalysts based on non-precious metals that can be utilized in various application scenarios.

Novel carbon nitride for efficient degradation of organic pollutants and value-added recycled plastics: synergistic effects of nitrogen vacancies and Fe

The introduction of nitrogen vacancies (VN) and iron (Fe) single atoms sites significantly enhances the visible light absorption and charge transfer ability of carbon nitride (CN) catalysts. This paper presents the successful synthesis of a VN-rich, Fe single atoms incorporated CN, a catalyst that demonstrates exceptional degradation performance and cycling stability. The 2-mercaptobenzothiazole (MBT) removal rate by 20Fe-CN reached 99.51% within just 11min under visible light, and the catalyst maintained superior photocatalytic performance upon repeated use. Additionally, the 20Fe-CN/Photo/High-temperature system effectively converted polystyrene (PS) to benzoic acid (BA), achieving a BA yield of 19.73% after 48hours. Under visible light irradiation, the VN sites captured electrons and facilitated their rapid transfer to neighboring Fe sites, enhancing the photocatalytic redox processes. This study also identified ·O2- as the primary active species in the photocatalytic process. This research supports the development of diverse single-atom modified carbon nitride photocatalysts, holding significant potential for wastewater treatment and plastic resource recycling, and providing valuable insights for future photocatalysts in environmental remediation.

Molecular Evidence for the Axial Coordination Effect of Atomic Iodine on Fe‐N4 Sites in Oxygen Reduction Reaction

AbstractWe present a molecular‐scale investigation of the axial coordination effect of atomic iodine on Fe‐N4 sites in the oxygen reduction reaction (ORR) by electrochemical scanning tunneling microscopy (ECSTM). A well‐defined model catalytic system with explicit and uniform iodine‐coordinated Fe‐N4 sites was constructed facilely by the self‐assembly of iron(II) phthalocyanine (FePc) on an I‐modified Au(111) surface. The electrocatalytic activity of FePc for the ORR shows notable enhancement with axial iodine ligands. The modulation of the electronic structure of Fe sites to evoke a higher spin configuration by axial iodine was evidenced. The interaction strength between oxygen‐containing species and active centers becomes weaker due to the presence of iodine ligands, and the reaction is thermodynamically preferable. Furthermore, the reaction dynamics of FePc on I/Au(111) were explicitly determined via in situ ECSTM potential pulse experiments. In contrast, axial atomic iodine was found inefficacious for improving the activity of Co‐N4 sites, and electron rearrangement was found to be marginal, demonstrating that adequate interactions between axial ligands and metal sites for optimizing electronic structures and catalytic behaviors are prerequisites for the impactful role of axial ligands.

High-Density Atomic Level Defect Engineering of 2D Fe-Based Metal-Organic Frameworks Boosts Oxygen and Hydrogen Evolution Reactions.

Electrocatalysts based on metal-organic frameworks (MOFs) attracted significant attention for water splitting, while the transition between MOFs and metal oxyhydroxide poses a great challenge in identifying authentic active sites and long-term stability. Herein, we employ on-purpose defect engineering to create high-density atomic level defects on two-dimensional Fe-MOFs. The coordination number of Fe changes from 6 to 4.46, and over 28% of unsaturated Fe sites are formed in the optimized Fe-MOF. In situ characterizations of the most optimized Fe-MOF0.3 electrocatalyst during the oxygen evolution reaction (OER) process using Fourier transform infrared and Raman spectroscopy have revealed that some Fe unsaturated sites become oxidized with a concomitant dissociation of water molecules, causing generation of the crucial *OH intermediates and Fe oxyhydroxide. Moreover, the presence of Fe oxyhydroxide is compatible with the Volmer and Heyrovsky steps during the hydrogen evolution reaction (HER) process, which lower its energy barrier and accelerate the kinetics. As a result, the optimized Fe-MOF electrodes delivered remarkable OER (259 mV at 10 mA cm-2) and HER (36 mV at 10 mA cm-2) performance. Our study offers comprehensive understanding of the effect of phase transformation on the electrocatalytic process of MOF-based materials.

Preventing Nitrite Desorption via Switching Hydrogenation Position: A Dual-Site Approach for Selective Nitrate Reduction to Ammonia.

The electrochemical nitrate reduction reaction (NO3RR), which converts harmful nitrates into valuable ammonia (NH3) with zero carbon emission, is one of the most promising alternatives to the Haber-Bosch process. However, the NO3RR process is complex and involves multiple proton-coupled electron transfers that generate intermediates or byproducts, such as NO2 -, resulting in low ammonia yields and faradaic efficiency (FE). Herein, by constructing a FeCu bimetallic catalyst (FeCu-NC), the hydrogenation position of *NO3 is switched at the FeCu dual-atom site, preventing the desorption of *NO2 intermediate. Furthermore, electron transfer from Cu to Fe sites mimics the electron flow direction in natural nitrite reductase enzymes and accelerates the reduction of *NO2 to NH3, achieving efficient conversion of NO3 - to NH3. A 24-hour electrocatalytic experiment with FeCu-NC demonstrates negligible NO2 - formation throughout the NO3RR process, with an ammonia production rate of 6.13mgh-1mgcat -1 and an impressive FE of 95%, which are remarkably superior in comparison to most of the NO3RR electrocatalysts. This work opens new avenues for the fundamental understanding of catalytic mechanisms and the development of next-generation catalysts for sustainable ammonia production.

Rigid Ligand Confined Synthesis of Carbon Supported Dimeric Fe Sites with High-Performance Oxygen Reduction Reaction Activity for Quasi-Solid-State Rechargeable Zn-Air Batteries.

Dimeric metal sites (DiMSs) in carbon-based single atom catalysts (SACs) offer distinct advantages in optimizing the adsorption energies of the catalytic intermediates and reaction pathways over single atom sites, which inspires the investigations on the rational design of DiMSs-based SACs and the accurate discernment of catalytic mechanisms. Here, dimeric Fe sites on carbon blacks (DiFe-N/CBs) are prepared using the precursor of metal-organic complex with a controlled structure, and the rigid ligand confinement secures the preservation of dimeric Fe sites during the thermal treatment. DiFe-N/CBs shows excellent electrocatalytic performance for oxygen reduction reaction (ORR) with a high half-wave potential of 0.917 V, and excellent durability with negligible activity decay. Theoretical studies reveal that the dimeric Fe sites have an optimal adsorption of OOH* with the Yeager-type binding, illustrating the advantages of DiMSs over SAs in catalyzing ORR. The rechargeable aqueous and quasi-solid-state Zn-air batteries assembled using DiFe-N/CBs-based air cathodes achieve small voltage gaps after long term charge/discharge test, showing great promises for practical applications. This synthetic strategy serves a novel platform to produce a scope of catalysts incorporating multimeric metal sites, and studies on the catalytic mechanism lay the foundation for establishing cooperative effect for multidentate adsorption reactions.

Rigid Ligand Confined Synthesis of Carbon Supported Dimeric Fe Sites with High‐Performance Oxygen Reduction Reaction Activity for Quasi‐Solid‐State Rechargeable Zn‐Air Batteries

AbstractDimeric metal sites (DiMSs) in carbon‐based single atom catalysts (SACs) offer distinct advantages in optimizing the adsorption energies of the catalytic intermediates and reaction pathways over single atom sites, which inspires the investigations on the rational design of DiMSs‐based SACs and the accurate discernment of catalytic mechanisms. Here, dimeric Fe sites on carbon blacks (DiFe‐N/CBs) are prepared using the precursor of metal‐organic complex with a controlled structure, and the rigid ligand confinement secures the preservation of dimeric Fe sites during the thermal treatment. DiFe‐N/CBs shows excellent electrocatalytic performance for oxygen reduction reaction (ORR) with a high half‐wave potential of 0.917 V, and excellent durability with negligible activity decay. Theoretical studies reveal that the dimeric Fe sites have an optimal adsorption of OOH* with the Yeager‐type binding, illustrating the advantages of DiMSs over SAs in catalyzing ORR. The rechargeable aqueous and quasi‐solid‐state Zn‐air batteries assembled using DiFe‐N/CBs‐based air cathodes achieve small voltage gaps after long term charge/discharge test, showing great promises for practical applications. This synthetic strategy serves a novel platform to produce a scope of catalysts incorporating multimeric metal sites, and studies on the catalytic mechanism lay the foundation for establishing cooperative effect for multidentate adsorption reactions.

Efficient electrocatalytic urea synthesis from CO2 and nitrate over the scale-up produced FeNi alloy-decorated nanoporous carbon

Electrocatalytic urea synthesis provides a favorable strategy for conventional energy-consuming urea synthesis, but achieving large-scale catalyst synthesis with high catalytic efficiency remains challenging. Herein, we developed a simple method for the preparation of a series of FeNi-alloy-based catalysts, named FeNi@nC-T (n represents the content of nanoporous carbon as 1, 3, 5, 7 or 9 g and T = 900, 950, 1000 or 1100 °C), for highly performed urea synthesis via NO3− and CO2 co-reduction. The FeNi@7C-1000 achieved a high urea yield of 1041.33 mmol h−1 gFeNi−1 with a Faradaic efficiency of 15.56% at –1.2 V vs. RHE. Moreover, the scale-up synthesized FeNi@7C-950-S (over 140 g per batch) was achieved with its high catalytic performance and high stability maintained. Mechanism investigation illuminated that the Ni and Fe sites catalyze and stabilize the key *CO and *N intermediates and minimize the C–N coupling reaction barriers for highly efficient urea synthesis.

Spin-Polarized PdCu-Fe3O4 In-Plane Heterostructures with Tandem Catalytic Mechanism for Oxygen Reduction Catalysis.

Alloying has significantly upgraded the oxygen reduction reaction (ORR) of Pd-based catalysts through regulating the thermodynamics of oxygenated intermediates. However, the unsatisfactory activation ability of Pd-based alloys toward O2 molecules limits further improvement of ORR kinetics. Herein, the precise synthesis of nanosheet assemblies of spin-polarized PdCu-Fe3O4 in-plane heterostructures for drastically activating O2 molecules and boosting ORR kinetics is reported. It is demonstrated that the deliberate-engineered in-plane heterostructures not only tailor the d-band center of Pd sites with weakened adsorption of oxygenated intermediates but also endow electrophilic Fe sites with strong ability to activate O2 molecules, which make PdCu-Fe3O4 in-plane heterostructures exhibit the highest ORR specific activity among the state-of-art Pd-based catalysts so far. In situ electrochemical spectroscopy and theoretical investigations reveal a tandem catalytic mechanism on PdCu-Fe3O4─Fe sites that initially activate molecular O2 and generate oxygenated intermediates being transferred to Pd sites to finish the subsequent proton-coupled electron transfer steps.