Adsorption Energy Of OH Research Articles

Lattice Mismatch Guided Nickel-Indium Heterogeneous Alloy Electrocatalysts for Promoting the Alkaline Hydrogen Evolution.

The immiscibility of crystallographic facets in multi-metallic catalysts plays a key role in driving the green H2 production by water electrolysis. The lattice mismatch between tetragonal In and face-centered cubic (fcc) Ni is 14.9 % but the mismatch with hexagonal close-packed (hcp) Ni is 49.8 %. Hence, in a series of Ni-In heterogeneous alloys, In is selectively incorporated in the fcc Ni. The 18-20 nm Ni particles have 36 wt % fcc phase, which increases to 86 % after In incorporation. The charge transfer from In to Ni, stabilizes the Ni0 state and In develops a fractional positive charge that favors *OH adsorption. With only 5 at% In, 153 mL h-1 H2 is evolved at -385 mV with mass activity of 57.5 A g-1 at-400 mV, 200 h stability at -0.18 V versus reversible hydrogen electrode (RHE), and Pt-like activity at high current densities, due to the spontaneous water dissociation, lower activation energy barrier, optimal adsorption energy of OH- ions and the prevention of catalyst poisoning.

Lattice Mismatch Guided Nickel‐Indium Heterogeneous Alloy Electrocatalysts for Promoting the Alkaline Hydrogen Evolution

AbstractThe immiscibility of crystallographic facets in multi‐metallic catalysts plays a key role in driving the green H2 production by water electrolysis. The lattice mismatch between tetragonal In and face‐centered cubic (fcc) Ni is 14.9 % but the mismatch with hexagonal close‐packed (hcp) Ni is 49.8 %. Hence, in a series of Ni−In heterogeneous alloys, In is selectively incorporated in the fcc Ni. The 18–20 nm Ni particles have 36 wt % fcc phase, which increases to 86 % after In incorporation. The charge transfer from In to Ni, stabilizes the Ni0 state and In develops a fractional positive charge that favors *OH adsorption. With only 5 at% In, 153 mL h−1 H2 is evolved at −385 mV with mass activity of 57.5 A g−1 at—400 mV, 200 h stability at −0.18 V versus reversible hydrogen electrode (RHE), and Pt‐like activity at high current densities, due to the spontaneous water dissociation, lower activation energy barrier, optimal adsorption energy of OH− ions and the prevention of catalyst poisoning.

Trace Mn-doped on highly dispersed Fe/Mn-SNC ultrathin carbon nanosheets for efficient oxygen reduction reaction

The design and development of non-noble metal carbon-based catalysts with efficient oxygen reduction activity remains a difficult problem. Here, Ultrathin two-dimensional carbon nano sheet catalyst Fe/Mn-SNC with rich pore structure doped with trace manganese was synthesized by simple sodium chloride template cracking method and freeze-drying method. Citric acid containing a large number of OH and COOH groups can provide multiple coordination sites for metal ions. In 0.1 M KOH solution, the Fe/Mn-SNC catalyst performed better than Pt/C in terms of ORR performance (E1/2 was 0.920 V vs RHE) and endurance (E1/2 fell roughly 5 mV after 10,000 cycles). The reaction path of the Fe/Mn-SNC was calculated through DFT calculation. It was found that a small amount of Mn doping would reduce the adsorption energy of OH*, the last step in ORR reaction, which was conducive to OH* falling off from the catalyst surface, reducing the potential barrier required for the reaction, and improving its ORR activity. This research offers fresh perspectives on the development of enhanced energy conversion as well as the design and synthesis of high-performance ORR catalysts.

Boosting Reactive Oxygen Species Generation Using Inter‐Facet Edge Rich WO3 Arrays for Photoelectrochemical Conversion

AbstractWater oxidation reaction leaves room to be improved in the development of various solar fuel productions, because of the kinetically sluggish 4‐electron transfer process of oxygen evolution reaction. In this work, we realize reactive oxygen species (ROS), H2O2 and OH⋅, formations by water oxidation with total Faraday efficiencies of more than 90 % by using inter‐facet edge (IFE) rich WO3 arrays in an electrolyte containing CO32−. Our results demonstrate that the IFE favors the adsorption of CO32− while reducing the adsorption energy of OH⋅, as well as suppresses surface hole accumulation by direct 1‐electron and indirect 2‐electron transfer pathways. Finally, we present selective oxidation of benzyl alcohol by in situ using the formed OH⋅, which delivers a benzaldehyde production rate of ≈768 μmol h−1 with near 100 % selectivity. This work offers a promising approach to tune or control the oxidation reaction in an aqueous solar fuel system towards high efficiency and value‐added product.

Boosting Reactive Oxygen Species Generation Using Inter-Facet Edge Rich WO3 Arrays for Photoelectrochemical Conversion.

Water oxidation reaction leaves room to be improved in the development of various solar fuel productions, because of the kinetically sluggish 4-electron transfer process of oxygen evolution reaction. In this work, we realize reactive oxygen species (ROS), H2 O2 and OH⋅, formations by water oxidation with total Faraday efficiencies of more than 90 % by using inter-facet edge (IFE) rich WO3 arrays in an electrolyte containing CO3 2- . Our results demonstrate that the IFE favors the adsorption of CO3 2- while reducing the adsorption energy of OH⋅, as well as suppresses surface hole accumulation by direct 1-electron and indirect 2-electron transfer pathways. Finally, we present selective oxidation of benzyl alcohol by in situ using the formed OH⋅, which delivers a benzaldehyde production rate of ≈768 μmol h-1 with near 100 % selectivity. This work offers a promising approach to tune or control the oxidation reaction in an aqueous solar fuel system towards high efficiency and value-added product.

NiSe2 Nanoparticles Supported on Halloysite Sheets as an Efficient Electrocatalyst toward Alkaline Oxygen Evolution Reaction

The oxygen evolution reaction (OER) with its sluggish kinetics has imposed a significant barrier to the sustainable and green generation of hydrogen fuel (via electrolysis of water) and the development of metal-air batteries. In this study, we report an efficient and novel OER electrocatalyst based on NiSe2 nanoparticles (NPs) and the naturally abundant halloysite clay mineral. The NiSe2/halloysite nanocomposite (NiSe2/H) was prepared by a simple one-step hydrothermal route. The electrocatalytic performance of the as-synthesized nanocomposite and its components (pristine NiSe2 and halloysite) toward OER in 1.0 KOH solution was examined. The NiSe2/H nanocomposite exhibited a significantly enhanced catalytic activity in OER, with a low overpotential of 235 mV (measured at the current density of 60 mA cm–2), a Tafel slope of 146 mV dec–1, and an outstanding long-term electrochemical durability for 16 h. Moreover, this nanocomposite required only 340 mV of overpotential to deliver the high current density of 250 mA cm–2. Further investigations revealed that the improved catalytic performance of NiSe2/H can be attributed to the increased number of active sites and the optimized adsorption energy of OH–. These results indicate that NiSe2/H is a promising non-precious metal-based catalyst for alkaline OER.

Polypyrrole-Assisted Ag Doping Strategy to Boost Co(OH)2 Nanosheets on Ni Foam as a Novel Electrode for High-Performance Hybrid Supercapacitors.

Battery-type electrode materials have attracted much attention as efficient and unique types of materials for hybrid battery supercapacitors due to their multiple redox states and excellent electrical conductivity. Designing composites with high chemical and electrochemical stabilities is beneficial for improving the energy storage capability of battery-type electrode materials. We report on an interfacial engineering strategy to improve the energy storage performance of a Co(OH)2-based battery-type material by constructing polypyrrole-assisted and Ag-doped (Ag-doped@Co(OH)2@polypyrrole) nanosheets (NSs) on a Ni foam using a hydrothermal process that provides richer electroactive sites, efficient charge transportation, and an excellent mechanical stability. Physical characterization results revealed that the subsequent decoration of Ag nanoparticles on Co(OH)2 nanoparticles offered an efficient electrical conductivity as well as a reduced interface adsorption energy of OH- in Co(OH)2 nanoparticles as compared to Co(OH)2@polypyrrole-assisted nanoparticles without Ag particles. The heterogeneous interface of the Ag-doped@Co(OH)2@polypyrrole composite exhibited a high specific capacity of 291.2 mAh g-1 at a current density of 2 A g-1, and showed a good cycling stability after 5000 cycles at 5 A g-1. The specific capacity of the doped electrode was enhanced approximately two-fold compared to that of the pure electrode. Thus, the fabricated Ag-doped@Co(OH)2@polypyrrole nanostructured electrodes can be a potential candidate for fabricating low-cost and high-performance energy storage supercapacitor devices.

Kinetics-favorable heterojunctional CNTs@CuCo-LDH/BPQD electrode with boosted charge storage capability for supercapacitor

Component modulation and structure construction are the fundamental strategies in designing electrode materials for supercapacitors. Layered double hydroxide (LDH) is considered the promising electrode material, while with the drawback of low electron transmission efficiency and pulverization hinder. Herein, a novel kinetics-favorable heterojunctional self-supporting film electrode, composed of carbon nanotubes (CNTs), CuCo-LDH, and black phosphorus quantum dots (BPQD), is successfully prepared and directly utilized as electrodes in the supercapacitor. Highly conductive CNTs evenly and heavily entangled with CuCo-LDH hollow structures, resulting in robust mechanical property, enhanced electrical conductivity, and accelerated charge transfer during a redox reaction. Together with the surface decorated high-carrier-mobility BPQD, constructing heterojunction and acting as an electron donor to provide numerous active sites and facilitate energy storage behavior, a promoted pseudocapacitive performance was obtained and furtherly demonstrated by the density functional theory simulations based on the adsorption energies of OH–. The as-fabricated CNTs@CuCo-LDH/BPQD electrode presents a maximum capacitance of 1061.6 F g−1. The as-assembled hybrid supercapacitor device represents energy density up to 62.1 Wh kg−1 and remarkable cycling performance with 79.1% capacity retention after 10,000 cyclic tests. The prototype supercapacitor of this work shed light on the engineering of LDH-based materials for practical energy storage devices.

Hollow cobalt selenide nanospheres wrapped with reduced graphene oxide nanosheets as electrodes for hybrid supercapacitor

In this work, hollow CoSe2 nanospheres wrapped with reduced graphene oxide (rGO) nanosheets are fabricated through combining the self-templated method with the electrostatic self-assembled method followed by heat treatment. The experimental results indicate that rGO nanosheets can act as space separator and structural protector to reduce the aggregation and nanoparticle size of hollow CoSe2 nanospheres and meanwhile maintain their structural integrity. Density functional theory calculations indicate that the wrapping of rGO nanosheets not only increases the electrical conductivity but also reduces the adsorption energy of OH– at the CoSe2/rGO interface. Accordingly, hollow CoSe2/rGO nanocomposites yield specific capacities of 757C g−1 at 3 A/g and 552C g−1 at 20 A/g, as well as a capacity retention of 92 % over 5000 cycles at 10 A/g. When coupled with N-doped carbon nanotube-based negative electrode, the fabricated HSC device delivers an energy density of 50.1 W h kg−1 at 800 W kg−1 as well as maintains a capacity retention of 94 % after 5000 cycles. Our work offers a further understanding of the charge storage mechanism of hollow CoSe2/rGO nanocomposites and may be extended to develop other advanced nanostructured metal selenides/graphene electrodes.

Tuning the catalytic activity of Ag7Au6 cluster for oxygen reduction reaction via support interactions

We investigate the suitability as oxygen reduction reaction (ORR) catalysts of Ag7Au6 clusters supported by nitrogen-doped graphene (N–graphene) sheets with two different nitrogen contents (3.61% and 8.43%), as well as TiO2(101) monolayers, using post–DFT methods. We employ two energetic descriptors (namely, the O2 and OH binding energies and O–O bond length), to compare the effect of two different supports on the catalytic activity of the Ag7Au6 cluster. We find that low adsorption energies for O2 (approximately −1 eV) and OH (below the one of its reaction on Pt), and O–O bond elongation (which reaches up to 1.34 Å in our study, corresponding to the superoxide bond length) cause the high ORR activity of our materials of interest. Our results show that the supported clusters have higher catalytic performance compared to the unsupported ones due to the lower binding energies of the O2 and OH molecules. Moreover, the TiO2(101) monolayer is a better support for the Ag7Au6 cluster, due to the O–O bond distance increasing up to 1.33 Å, facilitating O2 dissociation. In addition, the low (−0.35 eV) OH adsorption energy decreases the difficulty of OH removal. Through free energy calculations, we prove the ORR mechanism in acidic conditions to display an over-potential of −1.76 V, competitive with to the ones featured by currently available catalysts.

Construction of hierarchical sugar gourd-like (Ni,Co)Se2/(Ni,Co)Se2/CC nanostructure with enhanced performance for hybrid supercapacitor

Transitional metal selenides are regarded as promising electrode materials for battery-type electrodes on account of their superior electrical conductivity and high redox activity. It is expected to further improve their electrochemical performance by reasonable designing of the metal selenides’ components and construction of novel nanostructures. Thus, in this article, self-supported sugar gourd-like (Ni,Co)Se2/(Ni,Co)Se2 composites on carbon cloth are prepared by a facile approach. The theoretical calculations indicate that the (Ni,Co)Se2 has higher conductivity and larger adsorption energy of OH- than that of NiSe2 and CoSe2, thus effectively improving the kinetics of their electrochemical reactions. Thanks to synergetic effects from the active materials and their hierarchical nanostructures, the prepared sugar gourd-like (Ni,Co)Se2/(Ni,Co)Se2/CC nanoarrays achieve a high areal specific capacity of 1.278 mAh/cm2 (220.34 mAh/g) at 2 mA/cm2 and 88.9 % capacity retention after 5000 cycles. Furthermore, the flexible hybrid supercapacitor based on the designed nanocomposite demonstrates a high energy density of 0.7051 mWh cm−2 at the power density of 1.6303 mW cm−2 with extraordinary cycling stability. Such eminent energy storage performances strongly certificate that the obtained (Ni,Co)Se2/(Ni,Co)Se2/CC electrode is a potential battery-type electrode material for supercapacitor application.

Interfacial engineering of Ag nanoparticle-decorated polypyrrole@Co(OH)2 hetero-nanostructures with enhanced energy storage for hybrid supercapacitors

Battery-type electrode materials (BTEMs) still suffer from unsatisfactory actual specific capacities and cycling stability, which impede their applications in hybrid supercapacitors (HSCs). Herein, we report an interfacial engineering strategy to improve the energy storage performance of Co(OH)2-based BTEMs by constructing the polypyrrole (PPy)@Co(OH)2 @Ag hetero-nanostructures (HNs). In such HNs, Co(OH)2 nanosheets are initially grown onto PPy nanowires on Ni foam, which offer rich electroactive sites, efficient charge transport, and good mechanical stability. More importantly, density functional theory (DFT) calculation results indicate that the subsequent decoration of Ag NPs on Co(OH)2 nanosheets provides an enhanced electrical conductivity as well as a reduced surface adsorption energy of OH- at Co(OH)2 nanosheets compared to the PPy@Co(OH)2 HNs without the decoration of Ag NPs. Consequently, the prepared PPy@Co(OH)2 @Ag electrode material demonstrates a specific capacity of up to 277 mA h g−1 at 2 A g−1, 72 % capacity retention at 20 A g−1 together with a 92 % capacity retention over 5000 cycles at 10 A g−1. Furthermore, a HSC device using the PPy@Co(OH)2 @Ag as positive electrode has been fabricated to achieve an energy density of 54.4 W h kg−1 at 800 W kg−1. This work provides a new insight into the structural design of BTEMs for their applications in HSCs.

Mn2O3@Mn5O8 as an efficient catalyst for the degradation of organic contaminants in aqueous media through sulfite activation

Less-toxic, cost-effective, stable, and highly efficient catalysts for sodium sulfite (S(IV)) activation are required to degrade organic pollutants from wastewater. Herein, we report the facile thermal synthesis of Mn2O3@Mn5O8 that activates S(IV) more efficiently than other Mn and transition-metal oxides. Mn2O3@Mn5O8 exhibits good performance and long-term stability for eliminating various contaminants from aqueous media, including phenol, bisphenol A, nitrobenzene, 2,4-dichlorophenol, and acetaminophen. Its high performance is attributed to its multivalency, unique architecture, surface hydroxyl groups (–OH), and high surface area. X-ray diffractometry and high-resolution transmission electron microscopy revealed that Mn2O3@Mn5O8 comprises well-combined cubic Mn2O3 and monoclinic Mn5O8 crystalline structures, whereas electron paramagnetic resonance spectroscopy and scavenging tests showed that SO5•−, SO4•−, and •OH radicals are generated during S(IV) activation, with SO3•− as a precursor. The mixed-valence state provides effective and favorable electron transfer via Mn redox cycling (Mn(II) ↔ Mn(III) ↔ Mn(IV)), improving the S(IV) activation performance and catalytic activity. Mn2O3@Mn5O8/S(IV) system shows stable performance in the 3.0–7.0 pH range. Density functional theory calculations confirmed the higher catalytic activity as indicated by high –OH adsorption energy and significant inter-charge transformation. This study provides new insights and strategies for the activation of S(IV) using less-toxic metal oxides as catalysts and broadens the scope of heterogeneous Mn-based catalysts and S(IV) chemistry in real-world applications, particularly for the treatment of wastewater.

Benzenehexol-based 2D MOF as high-performance electrocatalyst for oxygen reduction reaction

Two-dimensional (2D) conductive metal–organic frameworks (MOFs) were an emerging class of potential oxygen reduction reaction (ORR) electrocatalysts to replace platinum-containing electrode materials. Herein, by first-principles calculations, we systematically studied the structural stability, electronic properties and ORR catalytic activity of metal-hexahydroxybenzene nanosheets, M3(C6O6), M = 3d and 4d transition metals. Based on formation energy, phonon spectrum and ab-initio molecular dynamics analyses, eight monolayer M3(C6O6) (M = Cr, Mn, Fe, Co, Cu, Zn, Ru and Rh) show superior thermodynamic, kinetic and thermal stabilities. Further ORR catalytic activity evaluation shown Cu3(C6O6) and Rh3(C6O6) had promising applications in catalyzing ORR 4e- pathway, with limiting potentials 0.76 and 0.80 V, respectively. The linear relationship between integrated crystal orbital Hamilton population (ICOHP) and ΔGOH∗ explains the suitable adsorption energy of OH* on the catalyst, resulting in the excellent ORR activity of Cu3(C6O6) and Rh3(C6O6). Our study on M3(C6O6) provides references for the research of other 2D MOFs as ORR catalysts.

One-Dimensional Co-Carbonate Hydroxide@Ni-MOFs Composite with Super Uniform Core-Shell Heterostructure for Ultrahigh Rate Performance Supercapacitor Electrode.

The insufficient contact between two phases in the heterostructure weakens the coupling interaction effect, which makes it difficult to effectively improve the electrochemical performance. Herein, a Co-carbonate hydroxide@ Ni-metal organic frameworks (Co-CH@Ni-MOFs) composite with super uniform core-shell heterostructure is fabricated by adopting 1D Co-CH nanowires as structuredirecting agents to induce the coating of Ni-MOFs. Both experimental and theoretical calculation results demonstrate that the heterostructure plays a vital role in the high performance of the as-prepared materials. On the one hand, the construction of super uniform core-shell heterostructure can create a large number of interfacial active sites and take advantages of the electrochemical characteristics of each component. On the other hand, the heterostructure can increase the adsorption energy of OH- ions and promote the electrochemical activity for improving the reversible redox reaction kinetics. Based on the aforementioned advantages, the as-fabricated Co-CH@Ni-MOFs electrode exhibits a high specific capacity of 173.1 mAh g-1 (1246 F g-1 ) at 1 A g-1 , an ultrahigh rate capability of 70.3% at 150 A g-1 and excellent cycling stability with 90.1% capacity retention after 10 000 cycles at 10 A g-1 . This study may offer a versatile design for fabricating a MOFs-based heterostructure as energy storage electrodes.

Nonmetallic Active Sites on Nickel Phosphide in Oxygen Evolution Reaction.

Efficient and durable catalysts are crucial for the oxygen evolution reaction (OER). The discovery of the high OER catalytic activity in Ni12P5 has attracted a great deal of attention recently. Herein, the microscopic mechanism of OER on the surface of Ni12P5 is studied using density functional theory calculations (DFT) and ab initio molecular dynamics simulation (AIMD). Our results demonstrate that the H2O molecule is preferentially adsorbed on the P atom instead of on the Ni atom, indicating that the nonmetallic P atom is the active site of the OER reaction. AIMD simulations show that the dissociation of H from the H2O molecule takes place in steps; the hydrogen bond changes from Oa-H⋯Ob to Oa⋯H-Ob, then the hydrogen bond breaks and an H+ is dissociated. In the OER reaction on nickel phosphides, the rate-determining step is the formation of the OOH group and the overpotential of Ni12P5 is the lowest, thus showing enhanced catalytic activity over other nickel phosphides. Moreover, we found that the charge of Ni and P sites has a linear relationship with the adsorption energy of OH and O, which can be utilized to optimize the OER catalyst.

Mechanism of Oxygen Reduction Reaction in Alkaline Medium on Nitrogen-Doped Graphyne and Graphdiyne Families: A First Principles Study.

Using extensive first principles protocols, a systematic investigation is performed to probe the oxygen reduction reaction (ORR) mechanism on nitrogen (N) doped graphynes (Gys, e. g. αGy, βGy, γGy and 6,6,12Gy) and graphdiyne (Gdy) in alkaline medium. We considered both associative and dissociative pathways, as well as two distinct intermediate forks for each of them depending on the first protonation site(s). Following the dissociative approach, the activation energy to form an O2 dissociated configuration is found as a function of the distances migrated by the O atoms over the catalyst surface and the amount of charge transferred from the C atoms linked to N. N doped αGy and 6,6,12Gy emerged as the best electrocatalyst comparing both pathways having lowest overpotentials of 0.88 and 0.82 V, respectively. The rate-limiting steps for the two different intermediate routes are observed to be dependent on the first protonation site(s) and related to the desorption of the OH radical from the sp hybridized C atom site(s) linked to N. Hence, the OH adsorption energy is identified as a descriptor for the efficiency of the ORR for the considered systems. The stabilities of the ORR intermediates are further elaborated in terms of pH and electrode potential.

Concave Pt-Zn Nanocubes with High-Index Faceted Pt Skin as Highly Efficient Oxygen Reduction Catalyst.

High dosage of expensive Pt to catalyze the sluggish oxygen reduction reaction (ORR) on the cathode severely impedes the commercialization of proton exchange membrane fuel cells. Therefore, it is urgent to cut down the Pt catalyst by efficiently improving the ORR activity while maintaining high durability. Herein, magic concave Pt–Zn nanocubes with high‐index faceted Pt skin (Pt78Zn22) are proposed for high‐efficiency catalysis toward proton exchange membrane fuel cells. These unique structural features endow the Pt‐skin Pt78Zn22/KB with a mass activity of 1.18 mA μgPt –1 and a specific activity of 3.64 mA cm–2 for the ORR at 0.9 V (vs RHE). Meanwhile, the H2–O2 fuel cell assembled by this catalyst delivers an ultrahigh peak power density of ≈1449 mW cm–2. Both experiments and theoretical calculations show that the electronic structure of the surface is adjusted, thereby shortening the length of the Pt–Pt bond and reducing the adsorption energy of OH*/O* on the Pt surface. This work demonstrates the synergistic effect of the oxidation‐resistant metal Zn and the construction of Pt‐rich surface engineering. Also, it guides the future development of catalysts for their practical applications in energy conversion technologies and beyond.

A fully-conjugated covalent organic framework-derived carbon supporting ultra-close single atom sites for ORR

Covalent organic frameworks linked by CC bonds have gained great attention for various application, and their fully conjugated skeletons were potentially conversed into two-dimensional (2D) carbons. Herein, we described a novel strategy to fabricate 2D carbon nanorods from a sp2 carbon linked COF, which had a high surface area of 804.8 m2 g−1. The one-dimensional channels confined the Fe ions during pyrolysis, which facilitated to form ultra-close atomic sites. The resulting catalyst displayed high catalytic activity towards oxygen reduction reaction, with a half-wave potential of 0.82 V and a mass activity of 4087.9 mA mg−1 at 0.7 V versus RHE, which were high than those of Pt/C (0.81 V and 126.3 mA mg−1). The theoretical calculation revealed the close FeN4 sites achieved a lower *OH adsorption energy than isolated FeN4 sites. This work provides a new insight into developing single atom catalysts from COFs.

Optimizing the Catalytic Activity of Pd-Based Multinary Alloys toward Oxygen Reduction Reaction.

The development of cost-effective catalysts for oxygen reduction reaction (ORR) has an enormous impact on fuel cells toward highly efficient low emission energy conversion. Recently, a Pt-free multinary PdAuAgTi alloy was discovered with excellent ORR activity and low overpotential close to that of Pt. To rationalize the experimental results, a model based on first-principles methods accelerated with deep learning is developed to rapidly compute and with high fidelity the *OH adsorption energy on the alloyed surface. The ensemble-average *OH adsorption energy is shown to explain the experimentally reported OER activities of PdAuAgTi and further is utilized to provide precise maps of the catalytic activity in the total composition space. Notably, the ORR activity of PdAuAgTi is found to be optimum in a narrow region of the composition space with 8-12 at. % Ti, which agrees with the experimental finding for enhanced ORR activity at 11-13 at. % Ti. In addition, replacing Au and Ag with the more cost-effective elements Cu and Zn is also shown to yield optimum catalysts for ORR. The current study shows that first-principles methods in conjunction with machine learning approaches are an effective tool for discovering multinary alloy systems for catalytic applications.