Electronic Metal-support Interactions Research Articles

Modulating the Electronic Metal‐Support Interactions in Single‐Atom Pt1−CuO Catalyst for Boosting Acetone Oxidation

The development of highly active single-atom catalysts (SACs) and identifying their intrinsic active sites in oxidizing industrial hazardous hydrocarbons are challenging prospects. Tuning the electronic metal-support interactions (EMSIs) is valid for modulating the catalytic performance of SACs. We propose that the modulation of the EMSIs in a Pt1 -CuO SAC significantly promotes the activity of the catalyst in acetone oxidation. The EMSIs promote charge redistribution through the unified Pt-O-Cu moieties, which modulates the d-band structure of atomic Pt sites, and strengthens the adsorption and activation of reactants. The positively charged Pt atoms are superior for activating acetone at low temperatures, and the stretched Cu-O bonds facilitate the activation of lattice oxygen atoms to participate in subsequent oxidation. We believe that this work will guide researchers to engineer efficient SACs for application in hydrocarbon oxidation reactions.

Suppressing byproduct formation for high selective CO2 reduction over optimized Ni/TiO2 based catalysts

One of the challenges for catalytic CO2 reduction is to control product selectivity, and new findings that can modify selectivity would be transformative. Herein, two kinds of TiO2 (homemade and commercial) with the same crystal phase but different surface properties are chosen as supports to prepare Ni-based catalysts for CO2 reduction, which show distinctly different product selectivity for CO2 reduction to CH4 or CO, as well as the CO2 conversion. The catalysts based on the homemade TiO2 support are highly selective for CH4 formation, while the latter ones are about 100% selective for CO formation under the same reaction conditions. In addition, the former ones are much active (more than 3 times) than the latter ones. We found that the collaborative contribution of Ti3+ and Ni2+ species and the electronic metal-support interactions effect maybe the main driving force behind for determining the product selectivity. Methane is almost exclusively produced over the catalysts with abundant Ti3+ and Ni2+ species and greater electronic metal-support interaction, otherwise, it will give priority to CO generation. The addition of CeO2 can reduce the Ni particle size and improve the dispersion of Ni nanoparticles, as well as create more Ti3+ species, contributing to the enhancement of CO2 conversion, but shows a negligible effect on product selectivity. Furthermore, the in situ DRIFT experiments and kinetic experiments indicate that the CO route is probably involved in the CO2 reduction process over the homemade Ni-CeO2/TiO2-CO catalyst with abundant Ti3+ and Ni2+ species and a strong electronic transform effect.

Triggering electronic coupling between neighboring hetero-diatomic metal sites promotes hydrogen evolution reaction kinetics

The emerging single atom catalysts (SACs) with tailorable, uniform and well-defined metal sites provide an ideal platform for studying the atomic-level correlation between structural configuration and catalytic behavior on heterogeneous catalysis. Here we demonstrate the electronic synergy of neighboring Ir and Ni diatomic sites on carbon supports (IrNi-N-C) for promoting the hydrogen evolution. The catalyst exhibits superior catalytic activity with low overpotentials (28 and 45 mV at 10 mA cm−2) and high turnover frequencies (TOFs, 3.06 and 1.40 H2 s−1 at 50 mV) in acidic and alkaline electrolytes, respectively. Theoretical and experimental results suggest that the incorporation of adjacent Ni-N4 moiety increases the occupancy of Ir 5d orbitals and shifts the d-band center down in the IrNi-N-C catalyst, thus facilitating the catalytic process by the optimal intermediate binding energy. This work highlights the significance of Ni 3d-Ir 5d electronic coupling between neighboring single metal sites for catalytic activity, and paves a way for the SACs design by manipulating d-d electronic interaction except for tuning of the coordination ligands and the electronic metal-support interactions.

Hierarchical porous cobalt/carbon hybrid anchored Ru-catalyzed ammonia-borane hydrolysis for efficient H2 release

Development of hierarchical architecture composed of heteroatom-doped porous carbon and earth-abundant transition metal for anchoring of noble metal nanoparticles (NPs) is essential but challengeable to improve catalytic performance for hydrogen production from ammonia-borane (AB) hydrolysis. In this study, we report the utilization of hierarchical porous nitrogen-doped carbon nanosheets encapsulated Co (Co-NC) synthesized by sodium chloride-template method for anchoring of Ru NPs toward hydrogen production from AB hydrolysis. The achieved Ru@Co-NC with an optimal Ru loading of 1.0 wt% delivers the highest catalytic activities with turnover frequencies of 568/1131 min−1 under aqueous/alkaline conditions at 25 ℃. The high performance for AB hydrolysis can be ascribed to the abundance of surface sites, fast mass/electron transfer and the electronic metal-support interaction between ultrafine Ru NPs and Co-NC, which facilitate the oxidative cleavage of the OH bonds in attacked H2O molecules (rate-determining step). Besides, this catalyst can be easily isolated by an external magnet and exhibits relatively good reusability with high maintained activity after five cycles. This work emphasizes the utilization of magnetically hierarchical architecture as support for noble metal NPs toward catalytic hydrogen generation.

Efficient Catalytic Elimination of CH3SH by a Wet-Piezotronics System over Ag Cluster-Deposited BaTiO3 with Electronic Metal–Support Interaction

Efficient Catalytic Elimination of CH₃SH by a Wet-Piezotronics System over Ag Cluster-Deposited BaTiO₃ with Electronic Metal–Support Interaction

Universal low-temperature oxidative thermal redispersion strategy for green and sustainable fabrication of oxygen-rich carbons anchored metal nanoparticles for hydrogen evolution reactions

A simple and green low-temperature oxidative thermal redispersion strategy was developed for obtaining well-distributed Rh, Ru, Ir NPs on oxygen-rich mesoporous carbon with considerable activity toward hydrogen evolution compared with the counterpart without any pre-treatment. • Universal low-temperature oxidative thermal redispersion strategy was developed. • The strategy benefits for well-defined metal NPs anchored on oxygenated carbons. • As-formed AC was a universal carrier for selected Pt group metal (Ru, Rh, Ir) NPs. • Rh/C-300A-350H had the highest HER activity for AB hydrolysis and water splitting. • The small Rh NPs with electron-rich sites contributed to the high HER performance. Supported metal nanoparticles (MNPs) have shown great promise in catalytic hydrogen evolutions because of the highly efficient utilization of metal atoms, while the low binding strength between MNPs and supports results in the agglomeration of MNPs into larger particles, considerably decreasing the catalytic efficiency. Herein, we smartly develop a universal, green, and sustainable low-temperature oxidative thermal redispersion strategy to fabricate metal oxide precursors and subsequently well dispersing and stabilizing MNPs (M = Rh, Ru, Ir) over oxygenated carbons (Mesoporous carbon, Ketjen black, and Vulcan carbon), which can be utilized as efficient catalysts for hydrogen production from ammonia borane (AB) hydrolysis and hydrogen evolution reaction (HER). Such flexible modulation strategy enables the formation of oxidized metal species on oxygenated carbons, which is the key to synthesize ultrasmall MNPs against sintering and agglomeration during the reduction process. Attributing to the innately structural/componential/surficial superiorities, the optimal Rh/C-300A-350H exhibits the highest catalytic activity toward hydrogen evolution from AB hydrolysis and HER with turnover frequencies of 3308/5040 min −1 in aqueous/basic solutions and an overpotential of 29 mV at 10 mA cm −2 in 1.0 M KOH, respectively. With the similar activation mechanism for dissociation of O–H bond in H 2 O, the highly dispersed Rh NPs with ultrafine sizes and electronic metal-support interaction are responsible for the excellent catalytic activity toward the hydrogen evolution reactions. This study presents an extremely facile and sustainable modulation strategy for increasing the adhesion of MNP catalysts on oxygenated carbons for catalytic applications.

Diffusion and Surface Segregation of Interstitial Ti Defects Induced by Electronic Metal–Support Interactions on a Au/TiO2 Nanocatalyst

Diffusion and Surface Segregation of Interstitial Ti Defects Induced by Electronic Metal–Support Interactions on a Au/TiO₂ Nanocatalyst

Single–atom Ir1 supported on rutile TiO2 for excellent selective catalytic oxidation of ammonia

Gaseous ammonia (NH3) in the atmosphere is potentially harmful to both human health and the environment. The selective catalytic oxidation of NH3 (termed as NH3–SCO) into N2 and H2O is a promising method for decreasing NH3 emissions. A highly efficient catalyst is required for controlling NH3 emissions by this method in practice. In this study, we prepared Ir/TiO2 catalysts using different crystal structures of TiO2 (rutile, P25 or anatase) as supports by a simple impregnation method and evaluated their performance in the NH3–SCO. We found that the Ir/TiO2–R (rutile) catalyst performed better than the Ir/TiO2–P25 (mixed–phase) and Ir/TiO2–A (anatase) catalyst. High–angle annular dark–field images of the aberration–corrected scanning transmission electron microscopy revealed that the Ir species were mainly atomically dispersed on the TiO2 support in Ir/TiO2–R with 1 wt% Ir loading, whereas the Ir species agglomerated to form clusters or nanoparticles in Ir/TiO2–P25 and Ir/TiO2–A. The combined results of X–ray absorption fine structure, H2–temperature–programmed reduction, and in situ diffuse reflectance for infrared Fourier Transform spectroscopy studies suggested that atomically dispersed Ir species had stronger electronic metal–support interaction with rutile TiO2, which resulted in easier to adsorb and activate O2 at the interface and thus, better low–temperature activity of the Ir/TiO2–R catalyst.

Nitrogen-doped carbon black supported synergistic palladium single atoms and nanoparticles for electrocatalytic oxidation of methanol

For commercially viable direct methanol fuel cells, electrocatalysts play a crucial role in motivating the sluggish methanol oxidation reaction (MOR) over anode. Unfortunately, the large-scale applications of current MOR catalysts are hampered by their poor tolerance to poisoning and fast activity degradation. Herein, a unique composite catalyst comprised of partial Pd nanoparticles and partial Pd single atoms (PdNPs/Pd-Nx@C) is developed. The as-fabricated catalyst exhibits remarkable activity of 9.45 mA·cm−2 towards MOR in alkaline solution, which is 7.05 and 3.92 times that of commercial Pd/C and nanoparticle type (PdNPs@C) electrocatalysts, respectively. Impressively, the PdNPs/Pd-Nx@C shows the highest long-time stability with 90.38% and 89.8% of the initial activity retained after 3600 s chronoamperometry (CA) test and 2000 cycles of cyclic voltammetry (CV) measurements with accelerated durability test (ADT), respectively. Combined with high-angle annular darkfield scanning transmission electron microscopy (HAADF-STEM), X-ray adsorption fine structure (XAFS) spectra and X-ray photoelectron spectroscopy (XPS) analyses, the superior performance of PdNPs/Pd-Nx@C can be ascribed to the synergistic effect from the Pd single atoms, N-doped carbon supports and Pd nanoparticles. Notably, the embedded Pd single atoms are liable to transfer electrons to the substrate due to the electronic metal-support interactions (EMSI) and the charge transfer between Pd nanoparticles and carbon supports is suppressed, inducing a weak adsorption strength of poisonous carbonous intermediate species on active Pd nanoparticles and improved poisoning tolerance in MOR process, which is verified by density functional theory (DFT) calculations as well as CO-stripping voltammetry experiments. This work not only contributes the first example of a synergistic catalyst between nanoparticles and single atoms for MOR but also deepens the knowledge on the metal-support interaction.

Manipulating the interfacial species on carbon nanospheres supported nanoparticulate Ru to boost the electronic metal−support interaction for enhancing selective hydrogenation of levulinic acid

Interfacial synergistic catalysis of supported metallic catalysts via engineering the electronic metal−support interaction (EMSI), i.e., manipulating the electronic/geometric configuration of interfacial sites, is an efficient strategy to promote their performances in structure-sensitive reactions, such as selective hydrogenation of levulinic acid (SHLA) to γ-valerolactone (GVL). Herein, carbon nanospheres (CNSs) with controlled morphology and tunable contents of surface carbonaceous species were facilely fabricated to support Ru nanoparticles (NPs). Combined with spectroscopic and microscopy characterizations, the EMSI between Ru and the special C = O species on interface of the Ru/CNSs catalysts was recognized, which contributed to the formation of small-sized Ru NPs with interfacial electron-deficient Ru (Ruδ+) sites. Such modulated electronic configuration of interfacial sites facilitated the H2 adsorption strength and capacity, eventually lowering the apparent activation energy (Ea) and boosting the intrinsic activity of Ru/CNSs in SHLA. A linearity between the turnover frequencies (TOFs) of levulinic acid (LA) and the contents of C = O species was demonstrated, substantiating the interfacial synergistic catalysis-mediated activity promotion evoked by enhancing the EMSI on Ru/CNSs.

Temperature-dependent selective nucleation of single-walled carbon nanotubes from stabilized catalyst nanoparticles

• Enriched (6,5) and (7,5) SWCNTs are respectively synthesized at ambient pressure. • Highly stabilized cobalt nanoparticles are generated from catalyst reduction. • Thermodynamic stability of different tube nuclei accounts for SWCNT selectivity. The utilization of metal nanoparticles supported on oxides substrate as a catalyst for rational single-walled carbon nanotube (SWCNT) growth is hindered by particle coarsening at high synthesis temperature, despite many empirical advances in supported catalyst design. In this study, a newly developed MgO-supported cobalt (Co-MgO) catalyst affords the formation of well-stabilized Co nanoparticles upon reduction, which is attributed to the electronic metal-support interaction and electrostatic stabilization at the Co-MgO interface. The highly stabilized Co nanoparticles led to the predominant growth of (6, 5) SWCNTs at 700 °C by CO disproportionation and the major SWCNT species was found to be (7, 5) SWCNTs at a reaction temperature of 800 °C. The temperature-dependent selective growth of the two SWCNT species was found, by density functional theory calculation, to be strongly correlated with the change of the relative thermodynamic stability of the SWCNT nuclei in the chirality assigning process at different temperatures.

Enhanced Catalytic Ozonation for Eliminating CH3SH via Stable and Circular Electronic Metal-Support Interactions of Si-O-Mn Bonds with Low Mn Loading.

Catalytic ozonation of methyl mercaptan (CH3SH) can effectively control this unbearable odorous sulfur-containing volatile organic compound (S-VOC). The construction of an electronic metal-support interaction (EMSI) coordination structure to maximize the number of active sites and increase the intrinsic activity of active sites is an effective means to improve catalytic performance. In this work, the abundant Si-OH groups on PSBA-15 (SBA-15 before calcination) were used to anchor Mn to form a Si-O-Mn-based EMSI coordination structure. Detailed characterizations and theoretical simulations reveal that the strong EMSI effect significantly adjusts and stabilizes the electronic structure of Mn 3d states, resulting in an electron-rich center on the Si-O-Mn bond to promote the specific adsorption/activation of ozone (O3) and an electron-poor center on the (Si-O-)Mn-O bond to adsorb a large amount of CH3SH accompanied by its own oxidative degradation. In situ Raman and in situ Fourier transform infrared (FTIR) analyses identify that catalytic ozonation over 3.0Mn-PSBA generates atomic oxygen species (AOS/*O) and reactive oxygen species (ROS/•O2-) to achieve efficient decomposition of CH3SH into CO2/SO42-. Furthermore, the electrons obtained from CH3SH in electron-poor centers are transferred to maintain the redox cycle of Mn2+/3+ → Mn4+ → Mn2+/3+ through the internal bond bridge, thus accomplishing the efficient and stable degradation of CH3SH prolonged to 180 min. Therefore, the rational design of catalysts with abundant active sites and optimized inherent activity via the EMSI effect can provide significant potential to improve catalytic performance and eliminate odorous gases.

Electronic Metal–Support Interaction Modulation of Single‐Atom Electrocatalysts for Rechargeable Zinc–Air Batteries

High-performance oxygen electrocatalysts play a key role in the widespread application of rechargeable Zn-air batteries (ZABs). Single-atom catalysts (SACs) with maximum atom efficiency and well-defined active sites have been recognized as promising alternatives of the present noble-metal-based catalysts for oxygen reduction reaction and oxygen evolution reaction. To improve their oxygen electrocatalysis activities and reveal the structure-activity relationship, many advanced synthesis and characterization methods have been developed to study the effects of 1)coordination and electronic structure of the metal centers and 2) morphology and stability of the conductive substrates. Herein, a detailed review of the recent advances of SACs with strong electronic metal-support interaction (EMSI) for rechargeable ZABs is provided. Great emphasis was placed on the EMSI forms and design strategies. Moreover, the importance and the impact of the atomic coordinating structure and the substrates on the oxygen electrocatalytic activity and stability are highlighted. Finally, future directions and perspectives on the development of SACs are also presented.

Gold Catalyst Anchored to Pre-Reduced Co3O4 Nanorods for the Hydrodeoxygenation of Vanillin Using Alcohols as Hydrogen Donors.

The preparation of highly dispersed metal catalysts with strong electronic metal-support interactions (EMSIs) is of great significance. In this study, oxygen vacancies (OVs) were generated on the surfaces of Co3O4 nanorods (NRs) through NaBH4 treatment, and then the generated surface OVs were used to anchor gold clusters. The resulting catalyst was used for the hydrodeoxygenation (HDO) of vanillin based on transfer hydrogenation with alcohol donors. The conversion of vanillin and the selectivity to 2-methoxy-4-methylphenol (MMP) both reached 99% under the optimized reaction conditions, and these values were significantly higher than those obtained for the gold catalyst supported on the untreated Co3O4 NRs. The obtained results were verified by theoretical calculations and experimental data and confirmed the existence of strong EMSIs between the OV-enriched Co3O4 NRs (Co3O4 NRs-OVs) and the gold clusters, which allows electron transfer from the Co3O4 NRs to gold. Increasing the number of electrons on the gold surface can promote the catalytic hydrogen transfer of alcohol, in addition to selectively adsorbing the C═O group in vanillin to improve the selectivity toward MMP. This strategy based on the OV-anchoring of metals onto the surface of a support can be extended to other metals, thereby providing a promising method for the design of advanced and highly efficient metal catalysts.

Atomic ruthenium stabilized on vacancy-rich boron nitride for selective hydrogenation of esters

Constructing and taming metal–support interaction of atoms and/or clusters has emerged as a promising protocol to maximize the catalytic performance of noble metal-based materials. Here, we report atomic ruthenium (Ru) with the oxidized state immobilized on defect-rich hexagonal boron nitride (d-BN) nanosheets and the essential interfacial electronic effect on Ru deduced from B- and N-vacancies for superior selective hydrogenation of esters. Experimental results indicate that strong electronic interplay exists between vacancies and atomic Ru species. Unlike defect-free commercial hexagonal BN (h-BN), d-BN can highly stabilize the active Ru species in atomic scale with oxidation state, and the obtained Ru/d-BN significantly increases the catalytic activity and durability. Specifically, the turnover frequency of Ru/d-BN is more than one order of magnitude higher than that of the conventional optimized Ag/SiO2 catalyst for the selective hydrogenation of dimethyl oxalate to methyl glycol. Systematic characterizations show that the Ru on B- and N-vacancies, and the defective BN serves as electron acceptor. The findings demonstrate the overall electronic effect on the electron-rich feature of Ru on d-BN, such that the electronic metal–support interactions cause the Ru species to favor the adsorption and selective scission of C–O bonds in esters, revealing a highly efficient hydrogenation catalysis.

Metal–Support Interactions in Metal/Oxide Catalysts and Oxide–Metal Interactions in Oxide/Metal Inverse Catalysts

Solid catalysts usually consist of multicomponents, within which interfacial interactions have been recognized as a key factor affecting structures and catalytic performance. Metal–support interactions (MSI) have been extensively studied in oxide-supported metal catalysts (metal/oxide catalysts), in which the important concepts of strong metal–support interactions (SMSI) and electronic metal–support interactions (EMSI) have been well established and their effects on the metal catalysis have been extensively demonstrated. Recently, metal-supported oxide inverse catalysts (oxide/metal inverse catalysts) have emerged as a new type of efficient catalysts, in which the oxide–metal interactions (OMI) strongly influence the oxide catalysis. Herein we comprehensively review the progresses on the MSI of metal/oxide catalysts and OMI of oxide/metal inverse catalysts with aims to emphasize structure sensitivity of MSI and OMI and to introduce the concepts of electronic oxide–metal interactions (EOMI) and electronic oxide–metal strong interactions (EOMSI) in oxide/metal inverse catalysts, in analogy to the concepts of EMSI and SMSI in metal/oxide catalysts. First, we briefly introduce the background of the topic and the interfacial interactions between metals and oxides with emphasis on the nature of metal–support interfacial interactions depending on the electronic structures. Second, the MSI, with an emphasis on the EMSI and SMSI, in metal/oxide catalysts is reviewed with an emphasis on the recently exported size and facet effects on the electronic structures and MSI. Third, the OMI in oxide/metal inverse catalysts is reviewed with an emphasis on introducing the EOMI and EOMSI. Finally, a summary and outlook is given with emphasis on the local nature and structure sensitivity of MSI and OMI.

Interfacial electronic structure modulation of Pt-MoS2 heterostructure for enhancing electrocatalytic hydrogen evolution reaction

The electronic metal-support interaction (EMSI) of heterogenous catalysts has attracted much attention for its enhancing electrocatalytic efficiency by impacting adsorption and desorption energy of reaction intermediates. Herein, we synthesize the monodispersed single-crystal Pt nanoparticles (~3 nm) decorated on MoS2 nanosheets with 2 H phase (Pt-MoS2) by a universal wet chemical method. The morphology and structure characterizations show that the loaded Pt single-crystals are approximately half truncated octahedral shapes enclosed by {1 1 1} and {2 0 0} facets. Benefitting from interfacial electronic structure modulation, the Pt-MoS2 exhibits a lower overpotential (67.4 mV at the current desity of 10 mA·cm−2), smaller Tafel slope (76.2 mV·dec−1), and robuster HER durability than those of pristine MoS2 nanosheets and prepared Pt NPs. The theoretical simulations further reveal that the Pt atom at the interface, which belong to {2 0 0} facets and adjoin S atoms, own the smallest hydrogen adsorption free energy by manipulating the d-band center of the Pt metal surface. This work provides crystalline structure and electronic configuration engineering strategy towards to design and develop of metal-support heterostructure with high HER activity and stability.

Understanding and application of metal-support interactions in catalysts for CO-PROX.

Preferential oxidation of carbon monoxide (CO-PROX) plays a vital role in H2 purification in the upstream systems of proton exchange membrane fuel cells (PEMFCs) for its high efficiency, low cost and practicability. The key to the application of CO-PROX is the design and preparation of catalysts, and the supported metal catalysts have been the mainstay after decades of development. The metal-support interaction (MSI), which acts as a bridge between the design of supported catalysts and atomic-level theoretical research, has triggered increasing attention. There is a growing body of literature that recognizes the importance of the MSI in heterogeneous catalysis. In this review, the impacts of the MSI including strong metal-support interactions and electronic metal-support interactions on the essential characteristics of supported single atom, nanocluster and nanoparticle catalysts, and therefore, on catalytic behaviors were discussed, respectively, primarily focusing on electron transfer, chemical bonding and the encapsulation of active sites induced by the MSI. We also presented an overview of how the MSI can be utilized to rationally design catalysts to meet target requirements such as high activity, selectivity or stability via appropriate selection and modification of support and active species. The perspectives of the future development for comprehensive understanding of the MSI were also proposed.

Strong electronic metal-support interaction between Pt and stainless mesh for enhancing the hydrogen evolution reaction.

Strong electronic metal-support interaction (EMSI) can tailor the electronic structure of electrocatalysts. Herein, Pt nanoparticles anchored on stainless mesh (SM) via EMSI engineering are reported, exhibiting excellent hydrogen production activity. Theoretical calculations demonstrate that the superior performance stems from the strong EMSI between Pt atoms and Fe atoms in SM.

Electronic metal-support interaction constructed for preparing sinter-resistant nano-platinum catalyst with redox property.

Generally, support materials with particular structural properties could effectively anchor metal nanoparticles and provide lower activation barriers in heterogeneous catalysis. To tailor the structure of stable iron oxide, NiFe2O4 of inverse spinel structure was obtained by combining nickel with iron element under an alkaline environment and high-temperature calcination. The p-type conductivity of NiFe2O4 provides the possibility of constructing electronic interfacial interaction with Pt nanoparticles by electron transfer. The constructed metal-support interaction could effectively stabilize Pt nanoparticles and be further enhanced during long-term harsh calcination (700 °C for 48 h) even under an O2 atmosphere. Meanwhile, the abundant structural defects of NiFe2O4 are beneficial for constructing low-temperature redox centers with the aid of Pt nanoparticles. Pt/NiFe2O4 exhibited not only excellent activity in room-temperature oxidation (CO and HCHO) and reduction reactions (chemo-selective hydrogenation of nitroarenes), but also high stability even after storage for more than 6 months. A self-adjusting mechanism triggered by structural defects is disclosed by in situ characterization and systematic reaction results. This work demonstrates an alternative concept to construct sinter-resistant and highly-effective nano-platinum catalysts robust for oxidation and reduction reactions.