Multimetallic Catalysts Research Articles

Balancing Activity and Stability through Compositional Engineering of Ternary PtNi-Au Alloy ORR Catalysts.

Achieving the optimal balance between cost-efficiency and stability of oxygen reduction reaction (ORR) catalysts is currently among the key research focuses aiming at reaching a broader implementation of proton-exchange membrane fuel cells (PEMFCs). To address this challenge, we combine two well-established strategies to enhance both activity and stability of platinum-based ORR catalysts. Specifically, we prepare ternary PtNi-Au alloys, where each alloying element plays a distinct role: Ni reduces costs and boosts ORR activity, while Au enhances stability. A systematic comparative analysis of the activity-stability relationship for compositionally tuned PtNi-Au model layers, prepared by magnetron co-sputtering, was conducted using a diverse range of complementary characterization techniques and electrochemistry, supported by density functional theory calculations. Our study reveals that a progressive increase of the Au concentration in the Pt50Ni50 alloy from 3 to 15 at % leads to opposing catalyst activity and stability trends. Specifically, we observe a decrease in the ORR activity accompanied by an increase in catalyst stability, manifested in the suppression of both Pt and Ni dissolution. Despite the reduced activity compared to PtNi, the PtNi-Au alloy with 15 at % Au still exhibits nearly three times the activity of monometallic Pt. It also demonstrates a significantly improved dissolution stability relative to that of the PtNi alloy and even monometallic Pt. These findings provide valuable insights into the intricate balance between activity and stability in multimetallic ORR catalysts, paving the way for the design of cost-effective and durable materials for PEMFCs.

Synergy strategy of multi-metals confined in heteroatom framework toward constructing high-performance water oxidation electrocatalysts

The development of a low-cost, highly active, and non-precious metal catalyst for oxygen evolution reaction (OER) is of great significance. Multi-metallic catalysts containing Fe, Co, and Ni exhibit remarkable OER activity, while the specific contributions of each component and the synergistic effects in the ternary metal catalyst has remained elusive. In this work, we synthesized a series of S and N-doped mono-metallic, bi-metallic, and tri-metallic hollow carbon sphere electrocatalysts (M−SNC) with the goal of enhancing the catalysts OER activity and shedding light on the unique roles and synergistic effects of the various metals in the FeCoNi ternary metal catalyst. Our systematic analyses demonstrated the introduction of Fe effectively reduces the overpotential, Co accelerates the kinetics of OER, and the addition of Ni further improves the OER performance. Benefiting from the synergistic effects, the FeCoNi-SNC exhibits a low overpotential of 270 mV, with no morphological or structural changes after reaction, maintaining high activity for 72 h at 10 mA cm−2. Moreover, the assembled FeCoNi-SNC || Pt/C water electrolysis device operates for 65,000 s with minimal degradation, demonstrating its potential for practical application. This work presents a synergy strategy for the preparation of low-cost and highly efficient OER catalysts and further provides insights into the rational design and preparation of multicomponent catalysts.

A very simple synthesis of defect-rich PdAg nanosponges for highly selective hydrogenation of furfural

Furfuryl alcohol (FA) is an important chemical and has extensive applications in varied fields. To realize the highly selective hydrogenation of furfural (FF) to produce FA, the key is the preparation of the catalysts with excellent performance. Herein, a very simple wet chemical method is developed for the one-step preparation of PdAg nanosponges (NSs). Specifically, with Pd(OAc)2 and AgNO3 as precursors, and ethylene glycol (EG) as both solvent and reducing agent, PdAg NSs can be grown and assembled at mild temperature of 40 °C. Throughout the reaction, no any surfactants and additional reducing agents are applied. The as-prepared PdAg NSs possess 3D self-supported alloy structures, “clean” surface, abundant pores, high specific surface area and rich defects. In the FF hydrogenation reaction at 60 °C under 1.5 MPa H2 pressure in the mixed solvent of ethanol and water (1 : 4 in volume ratio), the self-supported PdAg-1 NSs (1 : 1 in Pd/Ag molar ratio) exhibit superior catalytic performance than other PdAg NSs, pure Pd sample and commercial Pd/C (10%). With PdAg-1 NSs as catalyst in the absence of support, 100% FF can be converted and the selectivity toward FA is as high as 97.1% at 36.0 h of reaction. After 4 cycles, PdAg-1 NSs still maintain the high catalytic activity in FF hydrogenation and high selectivity toward FA, which may originate from the 3D self-supported structures, high specific surface area, “clean” surface, rich defects and electronic synergistic effect between Pd and Ag. This simple fabrication of PdAg NSs introduces new ideas for the synthesis of other nanostructured bi- and multi-metallic catalysts for highly selective FF hydrogenation to FA and other advanced applications.

Selective CO2 Reduction Electrocatalysis Using AgCu Nanoalloys Prepared by a "Host-Guest" Method.

Multimetallic nanoalloy catalysts have attracted considerable interest for enhancing the efficiency and selectivity of many electrochemically driven chemical processes. However, the preparation of homogeneous bimetallic alloy nanoparticles remains a challenge. Here, we present a room-temperature and scalable, host-guest approach for synthesis of dilute Cu in Ag alloy nanoparticles. In this approach, an ionic silver bromide precursor harboring exogenous Cu cations is reduced to yield ∼20 nm diameter AgCu alloy nanoparticles wherein the % Cu loading can be tuned precisely. AgCu nanoparticles with a 5% nominal loading of Cu exhibit peak activity (-0.23 mA/cm2 normalized partial current density) and selectivity (83.2% faradaic efficiency) for CO product formation from electrocatalytic reduction of CO2 at mild overpotentials. These AgCu nanoalloys exhibit a higher mass activity compared to Ag- and Cu-containing nanomaterials used for similar electrocatalytic transformations. Our host-guest synthesis platform holds promise for production of other nanoalloys with relevance in electrocatalysis and optics.

Catalysts for Liquid Organic Hydrogen Carriers (LOHCs): Efficient Storage and Transport for Renewable Energy.

Restructuring the current energy industry towards sustainability requires transitioning from carbon based to renewable energy sources, reducing CO2 emissions. Hydrogen, is considered a significant clean energy carrier. However, it faces challenges in transportation and storage due to its high reactivity, flammability, and low density under ambient conditions. Liquid organic hydrogen carriers offer a solution for storing hydrogen because they allow for the economical and practical storage of organic compounds in regular vessels through hydrogenation and dehydrogenation. This review evaluates several hydrogen technologies aimed at addressing the challenges associated with hydrogen transportation and its economic viablity. The discussion delves into exploring the catalysts and their activity in the context of catalysts' development. This review highlights the pivotal role of various catalyst materials in enhancing the hydrogenation and dehydrogenation activities of multiple LOHC systems, including benzene/cyclohexane, toluene/methylcyclohexane (MCH), N-ethylcarbazole (NEC)/dodecahydro-N-ethylcarbazole (H12-NEC), and dibenzyltoluene (DBT)/perhydrodibenzyltoluene (H18-DBT). By exploring the catalytic properties of noble metals, transition metals, and multimetallic catalysts, the review provides valuable insights into their design and optimization. Also, the discussion revolved around the implementation of a hydrogen economy on a global scale, with a particular focus on the plans pertaining to Saudi Arabia and the GCC (Gulf Cooperation Council) countries. The review lays out the challenges this technology will face, including the need to increase its H2 capacity, reduce energy consumption by providing solutions, and guarantee the thermal stability of the materials.

Optimizing bimetallic and multimetallic Cu-based catalysts by promoters for enhanced reverse Water-Gas Shift reaction: Insights and stability assessments

This study investigates bimetallic and multimetallic catalysts tailored for the reverse water gas shift (RWGS) reaction. Promoting with potassium and iron, while maintaining a constant copper content of 15 wt% on γ-alumina, revealed that bimetallic catalysts containing 7.5 wt% iron and 5 wt% potassium exhibit superior catalytic activity and stability. Among the multimetallic catalysts, the optimal composition was found to be in the 15 wt% Cu-5 wt% Fe-2.5 wt% K/γ-Al2O3 catalyst for the RWGS reaction. The prepared catalysts underwent assessments using various techniques such as N2 adsorption-desorption, XRD, H2-TPR, CO2-TPD, and FESEM. Stability assessments conducted over 72 hours showcased sustained long-term performance for the optimized catalysts, highlighting the influential role of the hierarchical structure. Mesopores extended the catalyst lifetime by reducing permeation limits, while macropores facilitated diffusion process, enhancing selectivity and stability. This hierarchical design also improved mass transfer, amplifying reaction rates. The synthesized catalysts exhibited exceptional specificity, demonstrating 100 % selectivity for the RWGS reaction. Particularly, under H2/CO2=1, these catalysts displayed remarkable carbon dioxide conversion rates, indicating potential for enhancing Cu-based catalysts in RWGS reactions by maximizing active sites.

Synchronously upgrading of hydrogen storage thermodynamic, kinetics and cycling properties of MgH2 via VTiMn catalyst

To effectively enhance the hydrogen storage performance of MgH2, the multimetallic catalyst VTiMn was triumphantly synthesized by mechanical alloying, and the MgH2-10 wt% VTiMn composite was further fabricated. The results revealed that VTiMn significantly improved the thermodynamic, kinetics and cycle properties of MgH2. Compared with pure MgH2, VTiMn promotes its plateau pressure to increase by 0.16 MPa and the initial desorption temperature to decrease by 47 K, showing obvious thermodynamic instability. Meanwhile, the MgH2-VTiMn composite can adsorb 5.5 wt% H2 within 72 s and release within 1200 s at 523 K. The activation energies of hydrogen absorption and desorption are 30.1 and 90.5 kJ/mol, respectively. After 130 cycles at 598 K, 83 % hydrogen capacity retention can still be achieved. Characterisation indicated that the composite formed a core–shell structure with MgH2 coated on the VTiMn surface. Part of the Mn element in VTiMn diffused into the Mg matrix, accompanied by the precipitation of nanoscale α-Mn particles at high temperature. The improved absorption kinetics can be attributed to the accelerated H atoms diffusion by the microcracks in VTiMn and the phase boundaries provided by the nano-precipitated phase, while the desorption kinetics benefits from the promotion of Mg nucleation and growth by α-Mn. Due to the effect of temperature, the rate-determining steps of the hydrogen absorption and desorption process of the composite at 598 K change from H atoms diffusion and Mg nucleation growth to H atoms surface penetration, respectively. These findings will facilitate a more comprehensive understanding of multimetallic catalysts.

Evaluation of individual metal contribution on active sites tailoring in multimetallic oxygen evolution catalytic system

Synergistic effects among different metals have positioned multimetallic electrocatalysts as promising facilitators for enhancing the oxygen evolution reaction (OER), though understanding their precise mechanisms has remained elusive. Delving into the unique contributions of individual metals is crucial for comprehending the complex synergy within multimetallic systems. In this study, we employed quinary (Co, Ce, Fe, Cu, and Mn) molybdates as a model to systematically investigate the role of each metal species in tailoring active sites. Our systematic analyses unveiled the presence of crucial oxygen vacancies, which can be considered as the active sites in OER. Comparative analyses of the top-performing quinary molybdates and their quaternary counterparts highlighted distinct electronic interactions and varying densities of oxygen vacancies, indicative of the diverse electron and vacancy engineering capabilities inherent to different metals. Mott-schottky plots demonstrated the predominant contribution of Mn to specific catalytic activity, followed by Ce, Fe, Cu, and Co. Leveraging an in-situ methanol probing method, it was found that the introduction of Cu, Ce, Fe, and Mn weakened intermediate adsorption, with Mn and Ce having the most significant effects, whereas Co strengthened adsorption. This work can advance our comprehension of the role played by individual metals within multimetallic catalysts, thereby promoting a more profound understanding of synergistic effects.

Accelerated Discovery of Multi-Metallic Nanostructured Catalysts for Anion Exchange Membrane Water Electrolyzers: Oxygen Evolution Reaction

The current reliance on platinum group metals (PGMs) as electrocatalysts for the oxygen evolution reaction (OER) in proton exchange membrane (PEM) water electrolyzers, the current industry standard, presents a significant barrier to the widespread adoption of hydrogen as a clean energy carrier. The scarcity and high cost of PGMs necessitate the development of alternative materials and technologies that offer comparable performance at a reduced cost. In this context, anion exchange membrane (AEM) water electrolyzers have emerged as a promising alternative.This presentation addresses this imperative by focusing on the design and synthesis of nanostructured mesoporous multi-metallic catalysts for AEM water electrolyzers, leveraging earth-abundant materials as alternatives to the rare and expensive PGMs currently employed in PEM water electrolyzers. Transition metal oxides, sulfides, and phosphides are promising candidates to replace PGMs, given their abundance, low cost, and tunable catalytic properties conducive to high OER activity. The OER activity and durability of newly developed multi-metallic transition metal catalysts in an alkaline environment will be discussed in this presentation.Preliminary results demonstrate that the developed catalysts exhibit high OER activity, achieving a potential of <1.5 V versus RHE at a current density of 10 mA cm⁻² in 1.0 M KOH. Notably, this surpasses the performance of commercial OER catalysts in alkaline environments. Furthermore, the catalyst exhibits superior durability, with < 0.5 mV/h potential loss over 100 h durability test at 10 mA cm⁻² in 1.0 M KOH.AcknowledgmentsThis work was supported by the U.S. Department of Energy (DOE), Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office (HFTO) under the auspices of the Electrocatalysis Consortium (ElectroCat 2.0). Argonne is managed for the U.S Department of Energy by the University of Chicago Argonne, LLC, under Contract DE-AC-02-06CH11357 .

Elucidating Pathways of Methanol Oxidation on Oxygen-Vacant NiOOH Sites Using a Synergistic in Situ Attenuated Total Reflectance Surface-Enhanced Infrared Absorption Spectroscopy and DFT Study

A thorough comprehension of the mechanism underlying the methanol oxidation reaction (MOR) on Ni-based catalysts is critical for electrocatalysis design and development of Ni-based alloys. However, the mechanism of MOR on these materials remains a matter of controversy. There have been few publications on employing surface enhanced spectroscopy to adequately capture the surface chemistry of MOR on NiOOH while the existing theoretical chemistry studies on the reaction mechanism presents a multitude of inconsistent and incomplete results. Here, we combine in situ surface-enhanced infrared absorption spectroscopy (SEIRAS) and density functional theory (DFT) to determine the mechanism and product distribution of MOR on monometallic Ni-based catalysts in alkaline media. Critically, the DFT calculations include the role of O-vacancy of NiOOH, which is argued to be the active site for methanol oxidation. The SEIRAS results show that two bands corresponding to nas(O=C–O) of HCOO- and nas(C–O) of HCO3 -/CO3 2- appears after the commencement of MOR and varies as a function of potentials. These spectroscopic results are in good agreement with the DFT-based energetics of reaction, suggesting that the MOR mainly proceeds in the following pathway: The early consumption of methanol yields HCOO- as the major product while increasing potentials stimulate further oxidation of adsorbed HCOO* to form HCO3 -/CO3 2-. On the other hand, we show a parallel pathway for the generation of HCO3 -/CO3 2- at high potentials that bypasses the formation of HCOO*. The two main pathways presented in this study are thermodynamically more feasible than the one predominantly reported in literature for MOR on NiOOH. The two former pathways circumvent CHO and/or CO to produce HCO3 -/CO3 2-, whereas the latter involves these species as intermediates. These DFT-based hypotheses are backed up by the spectroscopic evidence that no band associated with CHO and CO can be detected by SEIRAS. This study has the potential to offer invaluable atomic-level insights into MOR on NiOOH as a stepping stone to development of high-performance multi-metallic Ni-based catalysts. Figure 1

Green Catalytic Synthesis of Ethylenediamine from Ethylene Glycol and Monoethanolamine: A Review.

Ethylenediamine (EDA) is a crucial chemical raw material and fine chemical intermediate. Compared with the industrial approach of ammonolysis of 1,2-dichloroethane, the catalytic amination of ethylene glycol (EG) is an economical and environmentally benign route that will be the future trend for EDA synthesis. Herein, we systemically review the recent progress in direct and indirect catalytic conversion of EG to EDA. Furthermore, different types of catalysts are discussed: (i) supported metal and multimetallic catalysts, (ii) solid acid catalysts, and (iii) other active catalysts (e.g., ionic liquids and metal complexes). Finally, we conclude with the frontiers and future prospects of the catalytic synthesis of EDA from EG and monoethanolamine, providing readers a snapshot of this field.

Multi-metallic Layered Catalysts for Stable Electrochemical CO2 Reduction to Formate and Formic Acid.

Electrochemical CO2 reduction (ECR) to value-added products such as formate/formic acid is a promising approach for CO2 mitigation. Practical ECR requires long-term stability at industrially relevant reduction rates, which is challenging due to the rapid degradation of most catalysts at high current densities. Herein, we report the development of a bismuth (Bi) gas diffusion electrode on a polytetrafluoroethylene-based electrically conductive silver (Ag) substrate (Ag@Bi), which exhibits high Faradaic efficiency (FE) for formate of over 90 % in 1 M KOH and 1 M KHCO3 electrolytes. The catalyst also shows high selectivity of formic acid above 85 % in 1 M NaCl catholyte, which has a bulk pH of 2-3 during ECR, at current densities up to 300 mA cm-2. In 1 M KHCO3 condition, Ag@Bi maintains formate FE above 90 % for at least 500 hours at the current density of 100 mA cm-2. We found that the Ag@Bi catalyst degrades over time due to the leaching of Bi in the NaCl catholyte. To overcome this challenge, we deposited a layer of Ag nanoparticles on the surface of Ag@Bi to form a multi-layer Ag@Bi/Ag catalyst. This designed catalyst exhibits 300 hours of stability with FE for formic acid ≥70 % at 100 mA cm-2. Our work establishes a new strategy for achieving the operational longevity of ECR under wide pH conditions, which is critical for practical applications.

Mild Synthesis of Planar PdPtAuAgCuIr Nanocrystals with Granular Edges for Improved Ethanol Electrooxidation

AbstractWe report a mild, one‐pot synthesis of PdPtAuAgCuIr multimetallic nanocrystals with controlled shapes and explore their applications as the electrocatalysts for ethanol electrooxidation in alkaline medium. The success of current synthesis relies on the co‐reduction of six metal precursors in the presence of octadecylammonium chloride and ascorbic acid at an elevated temperature. The resulting products are featured with an in‐plane core‐shell structure, together with the trigonal/hexagonal plate decorated with granular edges. When serving as EOR electrocatalysts, the carbon‐supported PdPtAuAgCuIr nanocrystals exhibit more than five‐fold increase in mass activity as compared to that of commercial Pt/C, as well as improved reaction kinetics and long‐term durability. DFT calculations disclose that the reduced energy barrier renders the Pd‐based multimetallic catalyst in catalytic performance. The present study provides a feasible strategy to create multimetallic nanocrystals with controlled two‐dimensional morphology under ambient conditions, shedding light for rational design over advanced fuel cell catalysts composed of multimetallic alloy.

Pt-on-CoNi alloy nanoparticles supported on N and P co-doped graphene catalyst for highly efficient hydrogen evolution by acidic water electrolysis

The multimetallic catalysts with adjustable electronic structures and synergy effect between various metals compared to monometallic catalysts are widely applied in electrocatalysis. Herein, graphene is doped with N and P to prepare rGNP support, then a trimetallic PtCoNi/rGNP catalyst is prepared via simple impregnation and galvanic replacement reaction methods. Pt is highly dispersed on the CoNi alloy nanoparticles (NPs) on rGNP for PtCoNi/rGNP. Based on various characterization techniques and electrochemical testing results such as ICP-OES, XRD, XPS, TEM, HRTEM, STEM, STEM-EDX elemental mapping and line-scanning, it confirms the nanostructure of PtCoNi/rGNP (Pt-on-CoNi alloy). The overpotential of PtCoNi/rGNP for hydrogen evolution (HER) via acidic water electrolysis at 100 mA cm−2 is 15 mV, lower than commercial Pt/C (Pt/C) (66 mV). The Tafel slope of PtCoNi/rGNP is 6.46 mV dec−1, smaller than that of Pt/C (17.15 mV dec−1). The overpotential at 10 mA cm−2 only increases with 3.2 mV (reaching 13.2 mV) after a long time stability testing of 72 h, still lower than Pt/C (20 mV), indicating that it has high catalytic activity and stability. This work not only reveals the synergistic effect mechanism of noble metal-on-non-noble metal for the HER, but also provides a new strategy to develop efficient and highly stable catalysts for the HER.

Invigorating active sites for amorphous/crystalline heterophased co-based oxyhydroxide/tungstate toward enhanced electrocatalytic oxygen evolution: Trimetallic codoping-achieved synergistic regulation

Designing high-efficiency multimetal-based catalysts for oxygen evolution reaction at low overpotential is a grand challenge in alkaline water splitting due to the elusive synergistic effect between metal atoms. Blind pursuit of polymetallic miscibility cannot linearly enhance catalytic activity; instead, it incurs increased costs. Herein, we reported a facile trimetallic (Cu, Fe and La) codoping approach to tailor the electronic structure of Co-based oxyhydroxide/tungstate for boosting OER reaction. It was found that a better synergistic effect with Co can be exhibited only when Cu, Fe and La were coexisted in the catalyst. By virtue of this, the catalyst developed numerous oxygen vacancies, enhancing favorability for OER reaction and demonstrating high intrinsic activity. Systematic experiments additionally verified its improved reaction kinetics and optimized adsorption to intermediates. Ultimately, the prepared CoCuFeLa significantly reduced overpotential, decreasing by a minimum of 50 mV compared to monometallic doping. The alkaline electrolyzer based on the CoCuFeLa anode exhibited a low cell voltage of 1.53 V for water splitting. Remarkably, it experienced a substantial attenuation of 3.54 % after 150 h of continuous operation, attributing to the changes in the surface structure of the catalyst. This work provides a viable pathway for improving catalytic activity through multimetallic codoping, further promoting the design of more valuable multimetallic catalysts for hydrogen market.

High-throughput screening of multimetallic catalysts for three-way catalysis

High-throughput screening of multimetallic catalysts for three-way catalysis

To Be or Not To Be… Cooperative? Trimetallic Catalysts for the Ring‐Opening Polymerisation of Cyclic Esters

AbstractMultimetallic catalysts have emerged as a promising route to enhance catalyst performance in cyclic ester ring‐opening polymerisation (ROP), as these complexes can outperform the monometallic analogues in terms of reactivity and/or polymerisation control. Such enhancements are often attributed to “multimetallic cooperativity”, yet the origins of this cooperativity often remain unclear. Here, we report the synthesis and characterisation of two trimetallic Al‐salen complexes (L1(AlMe)3 and L1(AlEt)3), containing three Al‐salen subunits in close proximity, and their monometallic analogues (L2(AlMe) and L2(AlEt)). These complexes have been applied as catalysts for cyclic ester ROP under a range of conditions, to probe their potential for cooperative behaviour. Trimetallic L1(AlMe)3 and L1(AlEt)3 both display high activities in rac‐lactide ROP, giving kobs values of up to 11×10−3 min−1. Yet careful benchmarking against the monometallic complexes reveals that whether these systems display multimetallic cooperativity or not depends upon the reaction conditions. Detailed kinetic and spectroscopic studies into the origins of cooperativity revealed that the neighbouring metals play a key role in the initiation step, rather than propagation. Overall, these studies highlight the importance of understanding the reaction conditions in order to accurately define whether a catalyst displays multimetallic cooperativity.

Exploiting Multimetallic Cooperativity in the Ring-Opening Polymerization of Cyclic Esters and Ethers.

The use of multimetallic complexes is a rapidly advancing route to enhance catalyst performance in the ring-opening polymerization of cyclic esters and ethers. Multimetallic catalysts often outperform their monometallic analogues in terms of reactivity and/or polymerization control, and these improvements are typically attributed to "multimetallic cooperativity". Yet the origins of multimetallic cooperativity often remain unclear. This review explores the key factors underpinning multimetallic cooperativity, including metal-metal distances, the flexibility, electronics and conformation of the ligand framework, and the coordination environment of the metal centers. Emerging trends are discussed to provide insights into why cooperativity occurs and how to harness cooperativity for the development of highly efficient multimetallic catalysts.

A First-Principles Approach to Modeling Surface Site Stabilities on Multimetallic Catalysts

A First-Principles Approach to Modeling Surface Site Stabilities on Multimetallic Catalysts

A novel core-shell nanostructure of Ti-Au nanocrystal with PtNi alloy skin: Enhancing the durability for oxygen reduction reaction

The sluggish oxygen reduction reaction (ORR) at the cathode largely hinders the practical application of the proton-exchange membrane fuel cells (PEMFCs). Pt-based nanocrystals are the most effective electrocatalysts for the oxygen reduction reaction, however, suffer high cost, scarcity and unsatisfied durability. Herein, we report a new category of annealed multimetallic core-shell catalyst of gold core doped with titanium and platinum-nickel (PtNi) shell with Pt-rich surface as a highly active and robust electrocatalyst for ORR. The introduction of titanium can effectively stabilize the gold core, avoiding the outward migration of Au atoms and ensuring the exposure of Pt-Ni active sites. The experimental findings revealed that the annealed Ti-Au@PtNi NPs catalyst provides 19.26 and 9.84 times higher mass and specific activities than commercial Pt/C catalysts for the oxygen reduction reaction. Moreover, durability tests of annealed Ti-Au@PtNi NPs show no noticeable activity loss even after 20000 potential cycles between 0.6 and 1.0 V vs. RHE, demonstrating a promising catalyst for the oxygen reduction reaction.