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Prussian blue analogue (PBA)/metal-organic frameworks (MOFs) are multifunctional precursors for the synthesis of metal/metal compounds, carbon, and their derived composites (P/MDCs) in chemical, medical, energy, and other applications. P/MDCs combine the advantages of both the high specific surface area of PBA/MOF and the electronic conductivity of metal compound/carbon. Although the calcination under different atmospheres has been extensively studied, the transformation mechanism of PBA/MOF under hydrothermal conditions remains unclear. The qualitative preparation of P/MDCs in hydrothermal conditions remains a challenge. Here, we select PBA to construct a machine-learning model and measure its hydrothermal phase diagram. The architecture-activity relationship of substances among nine parameters was analyzed for the hydrothermal phase transformation of PBA. Excitingly, we established a universal qualitative model to accurately fabricate 31 PBA derivates. Additionally, we performed three-dimensional reconstructed transmission electron microscopy, X-ray absorption fine structure spectroscopy, ultraviolet photoelectron spectroscopy, in situ X-ray powder diffraction, and theoretical calculation to analyze the advantages of hydrothermal derivatives in the oxygen evolution reaction and clarify their reaction mechanisms. We uncover the unified principles of the hydrothermal phase transformation of PBA, and we expect to guide the design for a wide range of composites.
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The structural and superconducting properties of the Bi-based compound Bi2Pd3Se2 were investigated over a wide pressure range. The prepared Bi2Pd3Se2 sample was a superconductor with a superconducting transition temperature, Tc, of approximately 3.0 K, which differed from a previous report (Tc of less than 1.0 K). At ambient pressure, the powder X-ray diffraction (XRD) pattern of the Bi2Pd3Se2 sample was consistent with that previously reported for Bi2Pd3Se2. The Rietveld method was used to refine the crystal structure, which had a space group of C2/m (No. 12), as reported previously. This compound showed no clear anomaly due to the charge-density-wave (CDW) transition, as seen from the temperature dependence of magnetic susceptibility. However, the temperature dependence of electrical resistivity indicated a clear anomaly, presumably because of the CDW transition in the low-pressure range; the CDW transition temperature was approximately 230 K. The XRD patterns of the Bi2Pd3Se2 sample were measured at 0.160-22.7 GPa, and the patterns were well analyzed by both the Le Bail and Rietveld refinement methods, showing no structural phase transitions in the above pressure range. The pressure dependence of Tc of Bi2Pd3Se2 was recorded based on the temperature dependence of the electrical resistance, which showed an almost constant Tc at 0-13.7 GPa, and the Tc-pressure (p) behavior was fully discussed.
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The structural and superconducting properties of a Bi-based compound, Bi2Rh3Se2, are investigated over a wide pressure range. Bi2Rh3Se2 is a superconductor with a superconducting transition temperature, Tc, of 0.7 K. This compound is in a charge-density-wave (CDW) state below 240 K, which implies the coexistence of superconducting and CDW states at low temperatures. Here, the superconducting properties of Bi2Rh3Se2 are studied from the perspective of the temperature dependence of electrical resistance (R) at high pressures (p's). The pressure dependence of Tc of Bi2Rh3Se2 shows a slow increase in Tc at 0-15.5 GPa, and the Tc slowly decreases with pressure above 15.5 GPa, which is markedly different from that of normal superconductors because the value of Tc should simply decrease owing to the decrease in density of states (DOS) on the Fermi level, N(εF), driven by a simple shrinkage of the lattice under pressure. To ascertain the origin of such a dome-like Tc-p behavior, the crystal structure of Bi2Rh3Se2 was explored over a wide pressure range of 0-20 GPa on the basis of powder X-ray diffraction; no structural phase transitions or simple shrinkage of the lattice was observed. This result implies that the increase in Tc against pressure cannot simply be explained from a structural point of view. In other words, a direct relation between superconductivity and crystal structure was not found. On the other hand, the CDW transition became ambiguous at pressures higher than 3.8 GPa, suggesting that the Tc had been suppressed by the CDW transition in a low pressure range. Thus, the findings suggest that for Bi2Rh3Se2, Tc is enhanced through the suppression of CDW transition, which may be reasonable because the CDW-ordered state restrains the charge fluctuation to weaken the electron-phonon coupling and opens the gap to decrease the density of states on the Fermi level. The obtained dome-like Tc-p behavior indicates the possibility of Bi2Rh3Se2 being an exotic superconductor.
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Intermetallic compounds in the Al-Pt system were systematically studied via hard X-ray photoelectron spectroscopy, focusing on the positions of Pt 4f and Al 2s core levels and valence band features. On one hand, with increasing Al content, the Pt 4f core levels shift towards higher binding energies (BE), revealing the influence of the atomic interactions (chemical bonding) on the electronic state of Pt. On the other hand, the charge transfer from Al to Pt increases with increasing Al content in Al-Pt compounds. These two facts cannot be combined using the standard "chemical shift" approach. Computational analysis reveals that higher negative effective charges of Pt atoms are accompanied by reduced occupancy of Pt 5d orbitals, leading to the limited availability of these electrons for the screening of the 4f core hole and this in turn explains the experimentally observed shift of 4f core levels to higher BE.
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Electrocatalytic CO2 reduction via renewable electricity provides a sustainable way to produce valued chemicals, while it suffers from low activity and selectivity. Herein, we constructed a novel catalyst with unique Ti3 C2 Tx MXene-regulated Ag-ZnO interfaces, undercoordinated surface sites, as well as mesoporous nanostructures. The designed Ag-ZnO/Ti3 C2 Tx catalyst achieves an outstanding CO2 conversion performance of a nearly 100% CO Faraday efficiency with high partial current density of 22.59â mA cm-2 at -0.87â V versus reversible hydrogen electrode. The electronic donation of Ag and up-shifted d-band center relative to Fermi level within MXene-regulated Ag-ZnO interfaces contributes the high selectivity of CO. The CO2 conversion is highly correlated with the dominated linear-bonded CO intermediate confirmed by in situ infrared spectroscopy. This work enlightens the rational design of unique metal-oxide interfaces with the regulation of MXene for high-performance electrocatalysis beyond CO2 reduction.
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We report two novel three-dimensional copper-benzoquinoid metal-organic frameworks (MOFs), [Cu4 L3 ]n and [Cu4 L3 â Cu(iq)3 ]n (LH4 =1,4-dicyano-2,3,5,6-tetrahydroxybenzene, iq=isoquinoline). Spectroscopic techniques and computational studies reveal the unprecedented mixed valency in MOFs, formal Cu(I)/Cu(III). This is the first time that formally Cu(III) species are witnessed in metal-organic extended solids. The coordination between the mixed-valence metal and redox-non-innocent ligand L, which promotes through-bond charge transfer between Cu metal sites, allows better metal-ligand orbital overlap of the d-π conjugation, leading to strong long-range delocalization and semiconducting behavior. Our findings highlight the significance of the unique mixed valency between formal Cu(I) and highly-covalent Cu(III), non-innocent ligand, and pore environments of these bench stable Cu(III)-containing frameworks on multielectron transfer and electrochemical properties.
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Noble metals have an irreplaceable role in catalyzing electrochemical reactions. However, large overpotential and poor long-term stability still prohibit their usage in many reactions (e.g., oxygen evolution/reduction). With regard to the low natural abundance, the improvement of their overall electrocatalytic performance (activity, selectivity, and stability) was urgently necessary. Herein, strong metal-support interaction (SMSI) was modulated through an unprecedented time-dependent mechanical milling method on Pd-loaded oxygenated TiC electrocatalysts. The encapsulation of Pd surfaces with reduced TiO2-x overlayers is precisely controlled by the mechanical milling time. This encapsulation induced a valence band restructuring and lowered the d-band center of surface Pd atoms. For hydrogen peroxide electrosynthesis through the two-electron oxygen reduction reaction (ORR), these electronic and geometric modifications resulted in optimal adsorption energies of reaction intermediates. Thus, SMSI phenomena not only enhanced electrocatalytic activity and selectivity but also created an encapsulating oxide overlayer that protected the Pd species, increasing its long-term stability. This SMSI induced by mechanical milling was also extended to other noble metal systems, showing great promise for the large-scale production of highly stable and tunable electrocatalysts.
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The crystal structure and superconducting properties of a new type of titanium-pnictide superconductor, BaTi2(Sb1-yBiy)2O (y = 0.2, 0.5, and 0.8), are comprehensively investigated over a wide pressure range to elucidate the effect of substituting Bi for Sb on the superconducting behavior. The behavior of superconducting properties under pressure changes drastically with y, as expected from the double-dome Tc-y phase diagram obtained at ambient pressure. In this study, three BaTi2(Sb1-yBiy)2O samples (y = 0.2, 0.5, and 0.8) are considered, which correspond to the first superconducting dome, nonsuperconducting part, and second superconducting dome, respectively, in the Tc-y phase diagram. The crystal of BaTi2(Sb1-yBiy)2O with y = 0.2 shows a clear collapse transition, i.e., a drastic shrinkage of the lattice constant c at ca. 5 GPa. Strictly speaking, the collapsed crystal phase coexists with the noncollapsed phase above 5 GPa. On the other hand, BaTi2(Sb1-yBiy)2O with y = 0.8 shows a continuous change in the crystal lattice with pressure, i.e., no collapse transitions. The pressure dependence of Tc for BaTi2(Sb1-yBiy)2O with y = 0.2 shows a drastic increase in Tc at approximately 5 GPa, where the collapse transition occurs, indicating a clear pressure-induced superconducting phase transition related to the collapse transition. The value of Tc for BaTi2(Sb1-yBiy)2O with y = 0.8 increases slightly up to â¼2 GPa and is almost constant at 2-13 GPa. It is found that the superconducting behavior under pressure can be unambiguously classified by y based on the double-dome Tc-y phase diagram, indicative of distinguishable superconducting features at different y values. In this study, we comprehensively discuss the superconducting properties of the exotic material, BaTi2(Sb1-yBiy)2O, with a double-dome Tc-y phase diagram.
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The structural and superconducting properties of alkali-Bi-based compounds, KBi2 and RbBi2, were investigated over a wide pressure range for the first time. The samples of KBi2 and RbBi2 were prepared using a liquid ammonia (NH3) technique, and demonstrated superconductivity with superconducting transition temperatures, Tc, of 3.50 and 4.21 K at ambient pressure, respectively. The onset superconducting transition temperature, Tconset, of KBi2 decreased slightly; however, it suddenly jumped at 2 GPa and increased gradually with pressure, indicating the presence of two superconducting phases in the low-pressure range. The pressure-dependent X-ray diffraction patterns indicate that the KBi2 sample decomposed into KBi and Bi at pressures higher than 2.5 GPa. Moreover, a discontinuous change in Tconset was observed for KBi2 at 9 GPa, which reflects the decomposition of KBi2 into KBi and Bi. By contrast, the value of Tconset of RbBi2 was almost constant over a pressure range of 0-8 GPa. Thus, the superconducting properties and stability of alkali-Bi-based compounds against pressure were comprehensively explored in this study. In addition, the superconducting Cooper pair symmetry was investigated from the magnetic field dependence of Tc of KBi2 at 0.790 and 2.32 GPa, and of RbBi2 at 1.17 GPa, indicating the exact deviation from the simple s-wave paring model, which may be due to the complex electronic structure of Bi. The results elucidated the exotic superconducting properties of KBi2 and RbBi2 based on the pressure and magnetic field dependence of Tc and verified the chemical stability of KBi2 under pressure.
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Since the sluggish kinetic process of oxygen reduction (ORR)/evolution (OER) reactions, the design of highly-efficient, robust, and cost-effective catalysts for flexible metal-air batteries is desired but challenging. Herein, bimetallic nanoparticles encapsulated in the N-doped hollow carbon nanocubes (e.g., FeCo-NPs/NC, FeNi-NPs/NC, and CoNi-NPs/NC) are rationally designed via a general heat-treatment strategy of introducing NH3 pyrolysis of dopamine-coated metal-organic frameworks. Impressively, the resultant FeCo-NPs/NC hybrid exhibits superior bifunctional electrocatalytic performance for ORR/OER, manifesting exceptional discharging performance, outstanding lifespan, and prime flexibility for both Zn/Al-air batteries, superior to those of state-of-the-art Pt/C and RuO2 catalysts. X-ray absorption near edge structure and density functional theory indicate that the strong synergy between FeCo alloy and N-doped carbon frameworks has a distinctive activation effect on bimetallic Fe/Co atoms to synchronously modify the electronic structure and afford abundant dual-active Fe/Co-Nx sites, large surface area, high nitrogen doping level, and conductive carbon frameworks to boost the reversible oxygen electrocatalysis. Such N-doped carbon with bimetallic alloy bonds provides new pathways for the rational creation of high-efficiency energy conversion and storage equipment.
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We investigated the pressure dependence of electric transport in a superconducting sample, Ba0.77Na0.23Ti2Sb2O, to complete the phase diagram of superconducting transition temperature (Tc) against pressure (p). This superconducting sample exhibits a Tc value of 5.8 K at ambient pressure. Here, the superconductivity of the recently reported sample was investigated over a wide pressure range. The Tc value monotonously decreased with pressure below 8 GPa. Interestingly, the Tc value rapidly increased above 8 GPa and slowly declined with pressure above 11 GPa. Thus, a new superconducting phase was discovered above â¼9 GPa. The crystal structure of Ba0.77Na0.23Ti2Sb2O was also elucidated at 0-22.0 GPa with synchrotron X-ray powder diffraction. Consequently, an evident relation between the crystal structure and the superconductivity was revealed, namely, a clear structural phase transition was observed at 8-11 GPa, where the Tc value rapidly increased against pressure. This study provides detailed information on the superconductivity of Ba0.77Na0.23Ti2Sb2O under pressure, which will lead to a comprehensive understanding of pressure-driven superconductivity.
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Herein, we report the preparation and characterization of BaBi3 clarified by DC magnetic susceptibility, powder X-ray diffraction (XRD), and electrical transport. The superconducting properties of BaBi3 were elucidated through the magnetic and electrical transport properties in a wide pressure range. The superconducting transition temperature, Tc, showed a slight decrease (or almost constant Tc) against pressure up to 17.2 GPa. The values of the upper critical field, Hc2, at 0 K, were determined to be 1.27 T at 0 GPa and 3.11 T at 2.30 GPa, using the formula, because p-wave pairing appeared to occur for this material at both pressures, indicating the unconventionality of superconductivity. This result appears to be consistent with the topological non-trivial nature of superconductivity predicted theoretically. The pressure-dependent XRD patterns measured at 0-20.1 GPa indicated no structural phase transitions up to 20.1 GPa, i.e., the structural phase transitions from the α phase to the ß or γ phase which are induced by an application of pressure were not observed, contrary to the previous report, demonstrating that the α phase is maintained over the entire pressure range. Admittedly, the lattice constants and the volume of the unit cell, V, steadily decrease with increasing pressure up to 20.1 GPa. In this study, the plots of Tcversus p and V versus p of BaBi3 are depicted over a wide pressure range for the first time.
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A new superconducting sample, BaTi2Bi2O, was synthesized and characterized over a wide pressure range. The superconducting transition temperature, Tc, of BaTi2Bi2O was 4.33 K at ambient pressure. The crystal structure was tetragonal (space group of P4/mmm (No. 123)), according to the X-ray diffraction (XRD) pattern at ambient pressure. The XRD pattern was analyzed using the Le Bail method. The magnetic-field dependence of the magnetization at different temperatures was precisely investigated to elucidate the characteristics of the superconductivity. The pressure-dependent XRD patterns showed absence of structural phase transitions up to 19.8 GPa. The superconducting properties of BaTi2Bi2O were investigated under pressure. Tc monotonously increased with the pressure (p) up to 4.0 GPa and saturated above 4.0 GPa. The variations in the Tc-p plot were thoroughly analyzed. The Cooper pair symmetry (or superconducting pairing mechanism) was analyzed based on the magnetic field dependence of the superconductivity at ambient and high pressures, which indicated a sign of p-wave pairing for the superconductivity of BaTi2Bi2O, i.e., topologically nontrivial sign was suggested for BaTi2Bi2O.
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Semiconducting substances form one of the most important families of functional materials. However, semiconductors containing only metals are very rare. The chemical mechanisms behind their ground-state properties are only partially understood. Our investigations have rather unexpectedly revealed the semiconducting behaviour (band gap of 190â meV) for the intermetallic compound Be5 Pt formed at a very low valence-electron count. Quantum-chemical analysis shows strong charge transfer from Be to Pt and reveals a three-dimensional entity of vertex-condensed empty Be4 tetrahedrons with multi-atomic cluster bonds interpenetrated by the framework of Pt-filled vertex-condensed Be4 tetrahedrons with two-atomic polar Be-Pt bonds. The combination of strong Coulomb interactions with relativistic effects results in a band gap.
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Composite electrocatalysts have exhibited high activities toward water electrolysis, but the catalytically active sites really in charge of the reaction are still debatable while the conventional in situ X-ray spectroscopies are not capable of conclusively identifying the interaction of these materials with the electrolyte because of the complexity of catalysis. In this work, by utilization of operando Kß1,3 high-energy resolution fluorescence-detected X-ray absorption spectroscopy (HERFD-XAS) with a small incident angle, the operando quadrupole transition obviously showed that oxygen directly interacted with 3d orbitals of Co ions rather than that of Fe ions. Most importantly, Fe ions can promote the stabilization of the Co ions under a higher valent state during water oxidation, which may lead to a stable intermediate of reactant and its superior intrinsic activity. Accompanied by the first-principle calculations, the intermediates between 3d orbitals for surface Co ions and O 2p orbitals for the attaching hydroxide ions were ascribed to this orbital hybridization. Because of the unvaried structural features in conventional in situ techniques, operando HERFD-XAS revealed the remarkable change of chemical status to correlate with the orbital interaction rather than with the structural variation. This operando HERFD-XAS approach corresponding to the local orbital interaction in reactant/catalyst interface can potentially offer synergetic strategies toward realizing the chemical reactions or reaction pathways in various fields.
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Metal oxides of the spinel family have shown great potential towards the oxygen evolution reaction (OER), but the fundamental OER mechanism of spinel oxides is still far from being completely understood, especially for the role of the metal ions. Owing to various coordinated sites of divalent/trivalent metals ions and surface conditions (morphology and defects), it is a great challenge to have a fair assessment of the electrocatalytic performance of spinel systems. Herein, we demonstrated a series of MFe2O4 (M = Fe, Co, Ni, Zn) with a well-controlled morphology to achieve a comprehensive study of electrocatalytic activity toward OER. By utilizing several in situ analyses, we could conclude a universal rule that the activities for OER in the metal oxide systems were determined by the occurrence of a phase transformation, and this structural transformation could work well in both crystallographic sites (Td and Oh sites). Additionally, the divalent metal ion significantly dominated the formation of oxyhydroxide through an epitaxial relationship, which depended on the atomic arrangement at the interface of spinel and metal oxyhydroxide, while trivalent metal ions remained unchanged as a host lattice. The metal oxyhydroxide was formed during a redox reaction rather than being formed during OER. The occurrence of the redox reaction seems to accompany a remarkable increase in resistance and capacitance might result from the structural transformation from spinel to metal oxyhydroxide. We believe that the approaching strategies and information obtained in the present study can offer a guide to designing a promising electrocatalytic system towards the oxygen evolution reaction and other fields.
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Atomic-scale gold clusters were intercalated at the inter-facet corner sites of Pt-shell Ru-core nanocatalysts with near-monolayer shell thickness. We demonstrated that these unique clusters could serve as a drain of valence electrons in the kink region of the core-shell heterojunction. As jointly revealed by density functional theory calculations and valence band spectra, these Au clusters extract core-level electrons to the valence band. They prevent corrosion due to protonation and enhance the tolerance of CO by increasing the electronegativity at the outermost surface of the NCs during the methanol oxidation reaction (MOR). In these circumstances, the retained current density of Pt-shell Ru-core NCs is doubled in a long-term (2 hours) MOR at a fixed voltage (0.5 V vs. SCE) by intercalating these sub-nanometer gold clusters. Such novel structural confinement provides a possible strategy for developing direct-methanol fuel cell (DMFC) modules with high power and stability.
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A ternary catalyst comprising Iridium (Ir) single-atoms (SA)s decorated on the Co-oxide supported palladium (Pd) nanoparticles (denoted as CPI-SA) is developed in this work. The CPI-SA with 1 wt.% of Ir exhibits unprecedented high mass activity (MA) of 7173 and 770 mA mgIr -1, respectively, at 0.85 and 0.90 V versus RHE in alkaline ORR (0.1 m KOH), outperforming the commercial Johnson Matthey Pt catalyst (J.M.-Pt/C; 20 wt.% Pt) by 107-folds. More importantly, the high structural reliability of the Ir single-atoms endows the CPI-SA with outstanding durability, where it shows progressively increasing MA of 13 342 and 1372 mA mgIr -1, respectively, at 0.85 and 0.90 V versus RHE up to 69 000 cycles (3 months) in the accelerated degradation test (ADT). Evidence from the in situ partial fluorescence yield X-ray absorption spectroscopy (PFY-XAS) and the electrochemical analysis indicate that the Ir single-atoms and adjacent Pd domains synergistically promote the O2 splitting and subsequent desorption of hydroxide ions (OH-), respectively. Whereas the Co-atoms underneath serve as electron injectors to boost the ORR activity of the Ir single-atoms. Besides, a progressive and sharp drop in the ORR performance is observed when Ir-clusters and Ir nanoparticles are decorated on the Co-oxide-supported Pd nanoparticles.
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The construction of strong interactions and synergistic effects between small metal clusters and supports offers a great opportunity to achieve high-performance and cost-effective heterogeneous catalysis, however, studies on its applications in electrocatalysis are still insufficient. Herein, it is reported that W18 O49 nanowires supported sub-nanometric Ru clusters (denoted as Ru SNC/W18 O49 NWs) constitute an efficient bifunctional electrocatalyst for hydrogen evolution/oxidation reactions (HER and HOR) under acidic condition. Microstructural analyses, X-ray absorption spectroscopy, and density functional theory (DFT) calculations reveal that the Ru SNCs with an average RuRu coordination number of 4.9 are anchored to the W18 O49 NWs via RuOW bonds at the interface. The strong metal-support interaction leads to the electron-deficient state of Ru SNCs, which enables a modulated RuH strength. Furthermore, the unique proton transport capability of the W18 O49 also provides a potential migration channel for the reaction intermediates. These components collectively enable the remarkable performance of Ru SNC/W18 O49 NWs for hydrogen electrocatalysis with 2.5 times of exchange current density than that of carbon-supported Ru nanoparticles, and even rival the state-of-the-art Pt catalyst. This work provides a new prospect for the development of supported sub-nanometric metal clusters for efficient electrocatalysis.
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Fuel cells are considered potential energy conversion devices for utopia; nevertheless, finding a highly efficacious and economical electrocatalyst for the oxygen reduction reaction (ORR) is of great interest. By keeping this in view, we have proposed a novel design of a trimetallic nanocatalyst (NC) comprising atomic Pt clusters at the heterogeneous Ni(OH)2-to-Pd interface (denoted NPP-70). The as-prepared material surpasses the commercial J.M.-Pt/C (20 wt %) catalyst by â¼ 166 and â¼19 times with exceptionally high specific and mass activities of 16.11 mA cm-2 and 484.8 mA mgPt-1 at 0.90 V versus reversible hydrogen electrode (RHE) in alkaline ORR (0.1 M KOH), respectively. On top of that, NPP-70 NC retains nearly 100% performance after 10k accelerated durability test (ADT) cycles. The results of physical characterization and electrochemical analysis confirm that atomic-scale Pt clusters induce strong lattice strain (compressive) at the Ni(OH)2-to-Pd interface, which triggers the electron relocation from Ni to Pt atoms. Such charge localization is vital for O2 splitting on surface Pt atoms, followed by the relocation of OH- ions from the Pd surface. Besides, a sharp fall down in ORR performance (mass activity is 37 mA mgPt-1 at 0.90 V versus RHE) is observed when the Pt clusters are decorated on the surface of NiOx and Pd (denoted NPP-RT). In situ partial fluorescence yield mode X-ray absorption spectroscopy (PFY-XAS) was employed to reveal the ORR pathways on both configurations. The obtained results demonstrate that interface engineering can be a potential approach to boost the electrocatalytic activity of metal hydroxide/oxide-supported Pd nanoparticles and in turn allow Pd to be a promising alternative for commercial Pt catalysts.