Ni Atoms Research Articles

Mechanisms of Ni Dissolution from Ni-Rich Cathode in Li-Ion Batteries

Nickel-rich cathodes are the most promising candidates for realizing high-energy-density Li-ion batteries because of the high theoretical capacity. However, their structural instability detrimentally affects the battery performance during cell cycling, which restricts its large-scale commercial application. One impediment to their commercialization is the dissolution of transition metal ions, which can diffuse to the anode, corrupt the solid electrolyte interphase (SEI) films protecting the anode, and accelerate battery capacity fading. Here, we use ab initio molecular dynamics (AIMD) simulations to investigate the mechanism of Ni dissolution from the LiNiO2 cathode surfaces. Our calculations identified that the proton-transfer reactions between electrolytes and cathode surfaces cause the reduction of surface Ni atoms from Ni3+ to Ni2+, which weakened the Ni-O bonding. As the LiNiO2 cathode surface gets delithiated, more surface protonation reactions were observed, and the reduced Ni atoms were found to be dissolved from the cathode surfaces in the form of NiOOH, which is the fundamental origin of phase transition of LiNiO2 cathode from a layered to electrochemically inactive spinel-like structure, accompanied by H2O elimination and O2 evolution. Besides, we also studied the impact of various factors on Ni dissolution rates such as the presence of fluorine attachment and the coordination of Ni atoms and electrolyte species. These findings help inform future design of protective coatings, electrolytes, additives, and interfaces for Ni-rich cathode.

Influence of Transition-Metal Order of LNMO Spinel on the Li Ion Diffusion

Cathode materials contribute a substantial portion to the weight, cost, and environmentally sustainability of LIBs. A key strategy to enhance energy density at reduced cost and improved sustainability is to develop more cost-effective, cobalt-free, higher-energy-density alternatives. Among the Co-free electrode cathode chemistries, the LiNi0.5Mn1.5O4 (LNMO) spinel stands out as most promising. It exhibits a high specific energy density of 650 Wh/kg, attributed to its elevated operating voltage of approximately 4.7 V vs. Li+/Li. Furthermore, LNMO is more thermally stable than NMC and has high ionic conductivity. However, LNMO suffers from rapid capacity decay leading to short battery life, and high-voltage electrolytes that are resistant to decomposition at the higher operating voltages are required.LNMO forms two phases depending on the ordering of transition metals (TM). In the disordered phase, Ni and Mn ions are randomly distributed on the 16d sites of the Fd3̅m cubic unit cell, whereas in the ordered phase, the which Ni and Mn atoms occupy 4b sites and 12d sites of the P4332 cubic cell, respectively. In this work, the impact of TM ordering on fundamental parameters such as the unit cell size, electrode expansion, and Li-ion diffusion coefficients at different states of charge were explored using techniques such as in-operando x-ray diffraction, in-situ dilatometry, galvanostatic intermittent titration technique, and electrochemical impedance spectroscopy. The electrodes for these studies were prepared using both PVDF and water-based binders such as CMC in order to gain key insights into the effect of aqueous electrode processing on the Li+-ion transport parameters, interface resistances, and electrode expansion during cycling.

Tuning the Inter-Metal Interaction between Ni and Fe Atoms in Dual-Atom Catalysts to Boost CO2 Electroreduction.

Dual-atom catalysts (DACs) are promising for applications in electrochemical CO2 reduction due to the enhanced flexibility of the catalytic sites and the synergistic effect between dual atoms. However, precisely controlling the atomic distance and identifying the dual-atom configuration of DACs to optimize the catalytic performance remains a challenge. Here, the Ni and Fe atomic pairs were constructed on nitrogen-doped carbon support in three different configurations: NiFe-isolate, NiFe-N bridge, and NiFe bonding. It was found that the NiFe-N bridge catalyst with NiN4 and FeN4 sharing two N atoms exhibited superior CO2 reduction activity and promising stability when compared to the NiFe-isolate and NiFe-bonding catalysts. A series of characterizations and density functional theory calculations suggested that the N-bridged NiFe sites with an appropriate distance between Ni and Fe atoms can exert a more pronounced synergy. It not only regulated the suitable adsorption strength for the *COOH intermediate but also promoted the desorption of *CO, thus accelerating the CO2 electroreduction to CO. This work provides an important implication for the enhancement of catalysis by the tailoring of the coordination structure of DACs, with the identification of distance effect between neighboring dual atoms.

Elucidating the hydrogen adsorption mechanism in bare and TMs (Ni, Pd and Cd) decorated Al12P12, B12P12 and C24 nanocages for hydrogen storage via DFT study

This density functional theory investigation aims to assess the hydrogen adsorption potential of bare and metal catalysts (Ni, Pd, and Cd) decorated Al12P12, B12P12, and C24 nanocages for hydrogen storage applications. To find stability of the cages, cohesive energy and Atom-centered Density Matrix Propagation (ADMP) simulation is obtained. The computed adsorption energy (Ead) reveals the physisorption of H2 molecule in all bare cages. Thus, to improve hydrogen adsorption, Ni, Pd and Cd atoms are decorated in bare cages as a catalyst. After H and H2 adsorption in metal decorated cages, the highest Ead obtained is −3.49 and −0.91 eV in Ni decorated Al12P12 cages. The obtained gravimetric densities of ∼6 wt% for all Ni and Pd decorated Al12P12, B12P12, and C24 nanocages meet the Department of Energy (DOE) target. Hence, Ni and Pd catalysts decorated Al12P12, B12P12, and C24 nanocages are proposed as viable materials for hydrogen storage applications.

Ni3C/Ni3S2 Heterojunction Electrocatalyst for Efficient Methanol Oxidation via Dual Anion Co-modulation Strategy.

Enhancing active states on the catalyst surface by modulating the adsorption-desorption properties of reactant species is crucial to optimizing the electrocatalytic activity of transition metal-based nanostructured materials. In this work, an efficient optimization strategy is proposed by co-modulating the dual anions (C and S) in Ni3C/Ni3S2, the heterostructured electrocatalyst, which is prepared via a simple hot-injection method. The presence of Ni3C/Ni3S2 heterojunctions accelerates the charge carrier transfer and promotes the generation of active sites, enabling the heterostructured electrocatalyst to achieve current densities of 10/100mA cm-2 at 1.37V/1.53V. The Faradaic efficiencies for formate production coupled with hydrogen evolution approach 100%, accompanied with a stability record of 350h. Additionally, operando electrochemical impedance spectroscopy (EIS), in situ Raman spectroscopy, and density functional theory (DFT) calculations further demonstrate that the creation of Ni3C/Ni3S2 heterointerfaces originating from dual anions' (C and S) differentiation is effective in adjusting the d-band center of active Ni atoms, promoting the generation of active sites, as well as optimizing the adsorption and desorption of reaction intermediates. This dual anions co-modulation strategy to stable heterostructure provides a general route for constructing high-performance transition metal-based electrocatalysts.

Regulating the Ni-O bond length by constructing Ni(OH)2/CNTs heterostructure for enhanced nucleophile electrocatalytic oxidation

The electro-driven generation of the active Ni(OH)O species is crucial for the Ni(OH)2 to efficiently drive the nucleophilic oxidation reaction. However, the strategy to facilitate the generation of the Ni(OH)O species is only limited to the construction of the Pt/Ni(OH)2 heterostructures. In this study, carbon nanotubes (CNTs) are employed to reduce the dehydrogenation energy of the Ni(OH)2 by constructing Ni(OH)2/60CNTs heterostructures. The CNTs shorten the Ni-O bond length and increase the valence state of Ni atoms in Ni(OH)2, thus highly promoting the generation of Ni(OH)O. When the Ni(OH)2/60CNTs heterostructure is used for urea oxidation reaction, it displays highly enhanced catalytic activity relative to pure Ni(OH)2, attaining a current density of 10 mA cm−2 at 1.36 V versus reversible hydrogen electrode. This work provides a new strategy for reducing the dehydrogenation energy of the Ni(OH)2 and will inspire more research work on the recognition of the impact of metal–oxygen bond length on NOR activity.

Enhancing CO2 reduction with formamide-Ni@TiO2 catalyst

Formamide condensation with Ni can generate the NC structure, widely recognized as an efficient catalyst for electrocatalytic CO2 reduction reaction (CO2RR). To improve the utilization efficiency of Ni atoms, we introduced metal oxides as substrates to modulate the growth of a formamide-Ni (FA-Ni) condensate. FA-Ni@TiO2 demonstrated 2.8 times higher partial CO current density and Ni turnover frequency than FA-Ni, which were also higher than those of other FA-Ni@metal oxides, including ZrO2, Al2O3, Fe2O3, and ZnO. The improved performance of CO2RR can be attributed to the Ni content exposed on FA-Ni@TiO2 being twice that of the raw FA-Ni condensate. The Fourier transform infrared results suggested that formamide was adsorbed on TiO2 via the -CHO group, exposing -NH2 for potential interaction with Ni. As a result, Ni atoms were predispersed on the TiO2 surface. By contrast, the dispersion of Ni atoms was not enhanced by other metal oxides, such as Al2O3, Fe2O3, and ZnO, owing to the robust acidity of their surface sites. These metal oxides adsorbed formamide via -NH2, leading to the absence of extra -NH2 available for binding to Ni atoms. This study provides new insights into the development of appropriate substrates for single-atom catalysts.

Bis[μ-3-(pyridin-2-yl)pyrazolato]bis-[acetato-(3,5-dimethyl-1H-pyrazole)-nickel(II)

The title compound, [Ni2(C8H6N3)2(C2H3O2)2(C5H8N2)2] or [Ni(μ-OOCCH3)(2-PyPz)(Me2PzH)]2 (1) [2-PyPz = 3-(pyridin-2-yl) pyrazole; Me2PzH = 3,5-dimethyl pyrazole] was synthesized from Ni(OOCCH3)2·4H2O, 2-PyPzH, Me2PzH and tri-ethyl-amine as a base. Compound 1 {[Ni2(C30H34N10Ni2O4)]} at 100 K has monoclinic (P21/n) symmetry and the mol-ecules have crystallographic inversion symmetry. Mol-ecules of 1 comprise an almost planar dinuclear NiII core with an N4O2 coordination environment. The equatorial plane consists of N3,O coordination derived from one of the bidentate acetate O atoms and three of the N atoms of the chelating 2-PyPz ligand while the axial positions are occupied by neutral Me2PzH and the second O atom of the acetate unit. The Ni atoms are bridged by the nitro-gen atom of a deprotonated 2-PyPz ligand. Compound 1 exhibits various inter- and intra-molecular C-H⋯O and N-H⋯O hydrogen bonds.

Effective lifetime of Ni laser induced fluorescence excited at 336.9 nm during spark plug discharge

In this study, the laser induced fluorescence lifetime of Ni atoms in ambient air with presence of a plasma discharge was measured for the first time. Free Ni atoms were generated in air at a pressure of 1 bar by spark plug discharges driven by an inductive coil. The Ni atoms were excited at the 336.957 nm absorption line by a 336.96 nm, 90 ps laser pulse and the resulting temporally resolved decaying fluorescence signals were captured by a PMT. An effective fluorescence lifetime of about 1.1 ns was observed for the fluorescence signal within a 7.4 nm detection window centered at 345 nm. Further analysis also revealed that the lifetime of the transition showed statistically insignificant change throughout the duration of the discharge. The peak intensity of the fluorescence signal was found to be proportional to the integrated signal intensities. This in turn suggests that the integrated fluorescence signals in the aforementioned spectral region are proportional to the population density of ground state Ni atoms in the detection volume. The number density of free Ni atoms in the spark gap was measured over time during the plasma discharge, showing an accumulating trend in the beginning phase of the discharge followed by a slow decrease until the termination.

Fluorine-assisted asphalts waste carbonization to Ni-F-C electrocatalyst by mechanochemistry for efficient oxygen evolution

Low-cost Ni-F-C electrocatalysts were gram-scale synthesized through mechanochemical synthesis accompanied by asphalt and e-waste polytetrafluoroethylene (PTFE) upgrading. The high-value utilization of bulk industrial solid waste and the design of high-performance oxygen evolution electrocatalyst hold immense importance for sustainable environment and energy economy. The overpotential at 10 mA cm−2 (1 M KOH) for the optimized Ni-F-C catalyst was low as 269 mV. First, PTFE as a pore-forming agent generated plenty of pores inside the Ni-F-C catalyst (promoting mass transfer and surface wettability). Second, the structural self-reconstruction caused by fluorine migration made the electrode surface undergo in-situ transformation from Ni species to Ni-OOH/OH phase during OER. Additionally, DFT calculations demonstrated that the F atoms could trigger charge redistribution, effectively activate adjacent Ni atoms and reduce the energy barrier of the rate-determining step (*OH→*O). The migration of fluorine species and the infiltration of electrolyte combine to yield an increased number of active sites, improved conductivity and hydrophilicity, enhanced catalytic activity and durability.

Manipulation of Oxidation States on Phase Boundary via Surface Layer Modification for Enhanced Alkaline Hydrogen Electrocatalysis.

In alkaline water electrolysis and anion exchange membrane water electrolysis technologies, the hydrogen evolution reaction (HER) at the cathode is significantly constrained by a high energy barrier during the water dissociation step. This study employs a phase engineering strategy to construct heterostructures composed of crystalline Ni4W and amorphous WOx aiming to enhance catalytic performance in the HER under alkaline conditions. This work systematically modulates the oxidation states of W within the amorphous WOx of the heterostructure to adjust the electronic states of the phase boundary, the energy barriers associated with the water dissociation step, and the adsorption/desorption properties of intermediates during the alkaline HER process. The optimized catalyst, Ni4W/WOx-2, with a quasi-metallic state of W coordinated by a low oxygen content in amorphous WOx, demonstrates exceptional catalytic performance (22 mV@10mA cm-2), outperforming commercial Pt/C (30 mV@10mA cm-2). Furthermore, the operando X-ray absorption spectroscopy analysis and theoretical calculations reveal that the optimized W atoms in amorphous WOx serve as active sites for water dissociation and the nearby Ni atoms in crystalline Ni4W facilitated the release of H2. These findings provide valuable insights into designing efficient heterostructured materials for energy conversion.

Lignin-tailored fabrication of Ni single atom catalyst with Ni-N3 active site for efficient and selective catalytic transfer hydrogenation of lignin-derived aldehydes

Developing sustainable catalytic processes for catalytic transfer hydrogenation (CTHDO) of lignin-derived aldehydes to renewable fuels and chemicals is essential for scale valorization of vast underused lignin. Herein, the work contributes to the efficient and selective vanillin (VAN) CTHDO process using formic acid (FA) as the H-donor over a novel lignin-coordinated N-anchoring Ni single-atom catalyst (Ni SAs-N@LC). Ni SAs-N@LC was fabricated through facile pyrolysis of lignin-Ni/Zn complex mixed with melamine, in which lignin localized the Ni atoms through its negatively charged groups (e.g. phenolic OH) and the dispersed Ni atoms were further anchored by the N-doped carbon support to form Ni-N3 active structure. DFT calculations revealed that the Ni-N3 structure preferentially adsorbed the –CHO end of VAN and endowed the catalyst with superior hydrogen evolution capacity. Therefore, Ni SAs-N@LC exhibited outstanding catalytic performance (98.93% of VAN conversion and 97.3% of 2-methoxy-4-methylphenol selectivity) which was significantly higher than two reference catalysts Ni NPs@LC (without N-anchoring) and Ni@C (without lignin coordination and N-anchoring) as well as the previously reported Ni-based catalysts. Moreover, Ni SAs-N@LC presented excellent feasibility to the CTHDO of a wide range of lignin-derived aldehydes and exhibited superior cycling durability in FA system owing to its acid resistance property. Consequently, this work provides a facile preparation method for atomically dispersed biomass-based catalysts and further demonstrates its favorable applicability in the CTHDO of lignin-derived aldehydes.

Enhancement of anti-oxidation and tensile strength of nanotwinned Cu foils by preferential Ni electrodeposition

In this study, Ni was employed to enhance the mechanical properties of nanotwinned copper (NT-Cu) foils due to its excellent oxidation resistance and compatibility with Cu. The tensile strength of the NT-Cu foils was enhanced 12.6 % (752.8 to 847.3 MPa) by Ni co-electrodeposition. During the electroplating, it was found that Ni ions inhibited the Cu growth, causing the reduction potential (overpotential) to shift in the negative direction. It resulted in a reduced deposition rate and decreased the twin spacing of the foils. Additionally, Ni ions acted as impurities for the grain refinement. Time of flight secondary ion mass spectrometry (TOF-SIMS) results indicated that Ni atoms were deposited on the top and bottom of the foils due to the limiting current density of Ni. The NT-Cu-Ni exhibited low roughness and performed superior resistance to oxidation compared to the NT-Cu. X-ray photoelectron spectroscopy (XPS) was also utilized to characterize the oxidation of the Cu (Ni) alloys. These mechanisms contributed to high strength, low resistivity, and excellent oxidation resistance of the NT-Cu-Ni foils for future battery materials.

Structural Ni0-Niδ+ Pair Sites for Highly Active Hydrogenation of Nitriles to Primary Amines.

Supported metal pair sites have sparked interest due to their tremendous potential as bifunctional catalysts. Here, we report the structural Ni0-Niδ+ pair sites constructed in a well-defined nanocrystal phase of Ni3P. These Ni0-Niδ+ pair sites exhibited a remarkable product formation rate of 123 molBA/molmetal/h for the hydrogenation of benzonitrile (BN) to benzylamine (BA). The heterogeneity of surface Ni atoms over the Ni3P crystal created two types of metal centers, Ni0 and Niδ+, with a specific spatial distance of 4-5 Å. The Ni0 site acted as the center for H2 activation, while the Niδ+ site served as the adsorption and activation center for the C ≡ N group. The highly efficient cooperation effect of Ni0-Niδ+ pair sites resulted in a TOF of 2915 h-1 in BN hydrogenation, which is 2.4 and 9.7 times higher than that over the mono-Ni0 and -Niδ+ sites, respectively.

Straight sections of step edges on a NiAl(110) curved single crystal surface used to calculate an approximation of step formation energy

Curved crystals may feature a smooth transition between different vicinal surfaces. Using one curved single crystal to study different vicinal surfaces requires less experimental time than using several single flat crystals. Here, we study step distributions on the (110) plane of a curved NiAl single-crystal surface, which consists of alternating Ni and Al atom rows. We use scanning tunneling microscopy under UHV conditions at room temperature and our home-built Python-based analysis script to obtain statistical information on kink and straight sections along step-edge distributions from STM images. We perform this analysis mainly to study this single crystal’s kink distributions and step termination We propose a new method to estimate the step formation energy based on step edge analysis and statistical mechanics. With this method, we find an approximation of the step formation energy for NiAl(110).

Effect of CeO2@Ni on the Oxidation Resistance of in Situ TiC/Ni Composite Applied for Intermediate Temperature Solid Oxide Fuel Cell Interconnects

The TiC/Ni composites with different CeO2 or CeO2@Ni content are fabricated by pressureless reactive sintering, and the CeO2@Ni particles are prepared by electroless plating technique. The results show that the continuous Ni layer is prepared on CeO2 particles, leading to the decrease of contact angle between CeO2 and Ni from about 116° to 65°. The relative density of composites with 1 wt% CeO2 increases from 85.79% to 96.45% by Ni layer on CeO2 particles. The CeO2 or CeO2@Ni particles exhibit no obvious influence on the microstructure of composites, and Ce atoms of CeO2 diffuse into TiC particles during the reactive sintering process. The mass gain of composite decreases from 7.4709 to 4.9075 mg cm−2 by addition of 1 wt% CeO2@Ni. The Ce‐doped in NiO and TiO2 would restrict the inward diffusion of O atoms and outward diffusion of Ni atoms, resulting in the improvement of oxidation resistance of composite. With the increase of CeO2@Ni content from 0 to 1 wt%, the surface specific resistance of composite decreases from 3.16 to 0.56 Ω cm2 at 800 °C due to the thinner oxide scale and lower bandgap of TiO2 by Ce doping.

Study of Size Effect on Ni60Nb40 Amorphous Particles and Thin Films by Molecular Dynamic Simulations

Ni60Nb40 amorphous particles (APs) and amorphous thin films (ATFs) with various sizes were investigated by molecular dynamic simulations. It is revealed that sample size has effects on both Ni60Nb40 APs and ATFs composed of shell or surface and core components. Ni60Nb40 APs have an average bond length of 2.57 Å with major fivefold-symmetry atomic packing and low bond-orientation orders of Q6 and Q4 in both core and shell components. Ni atoms in Ni60Nb40 APs and ATFs prefer to segregate to the shell and surface regions, respectively. Atomic packing structure differences between various-sized Ni60Nb40 APs and ATFs affect their glass transition temperatures Tg, i.e., Tg decreases as the particle size or the film thickness decreases in Ni60Nb40 APs and ATFs, respectively. Our obtained results for Ni60Nb40 APs and ATFs clearly reveal a size effect on atomic packing and glass transition temperature in low-dimensional metallic glass systems.

Metallocorroles as bifunctional electrocatalysts for water-splitting: A theoretical investigation

Designing efficient electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is an important step of the water-splitting procedure, due to the expensive electrocatalysts and the energy loss because of overpotentials. Accordingly, in the present study and based on the newly synthesized copper-corrole complexes, several metallocorroles that can be used as electrocatalysts in water-splitting reaction were theoretically designed. The main objective of the present study is to investigate the electrocatalytic behavior of various metallocorroles toward OER at the anode as well as HER at the cathode. So, our focus will be on the corrole substrates incorporating Cr, Mn, Fe, Co, Ni, and Cu single atoms, nitrogen removal defective complexes, and Cl-functionalized corroles to explore the effect of structural modifications on the catalytic activity of metallocorroles. We found that the Ni- and Cr-corrole are encouraging catalysts for the OER and HER, respectively, outperforming the synthesized copper-based substrate and other designed metallocorroles with low overpotentials (ƞOER=0.68 V and ƞHER=0.10 V). The obtained Gibbs free energies confirm the feasibility of OER on a Ni single atom and HER on a Cr single atom of metallocorroles. The Volcano diagrams also reveal that the metallocorroles with better oxygen and hydrogen desorption correspond to the Ni- and Cr-corrole substrates, respectively. Generally, results show that our designed metallocorroles can be considered competent catalysts for water-splitting reactions.

Anchoring magic NiCo2O4/NiO on Ni foam as an effective and binder-free electrocatalyst for boosting hydrogen evolution reaction

Electrocatalysts that can sustain water splitting without corrosion are required for large-scale water electrolysis applications. Thus, designing and constructing stable electrocatalysts is known as a crucial role in hydrogen evolution reactions (HER). Herein, NiCo2O4/NiO nanocubes on Ni foam (NF) as a stable electrocatalyst were fabricated successfully by using a facile hydrothermal method. Field Emission Scanning Electron Microscopy (FESEM) confirms the formation of distinct magic NiCo2O4/NiO/NF nanocubes with a size of 50–150 nm. The electrochemical tests indicated that the NiCo2O4/NiO nanocubes possess long stability of about 140 h and exceptional HER activity with a low overpotential of 38 mV at a current density of 10 mA.cm−2 in a 1 M potassium hydroxide (KOH) and a Tafel slope of only 45 mV.dec−1. The obtained results indicated that this level of HER catalytic performance is assigned to the rough surface and synergistic interactions between Ni and Co atoms in the nanocubes. It was also determined that the existence of NiO interface layer causes robust adhesion between NF and NiCo2O4 nanocubes. In addition, this discovery points to an advantageous future for the configuration and synthesis of highly effective, non-precious metal-based electrocatalysts for large-scale hydrogen production via water-splitting.

DFT and machine learning studies on a multi-functional single-atom catalyst for enhanced oxygen and hydrogen evolution as well as CO2 reduction reactions

In this contribution, the design of a graphene-supported high-entropy single-atom catalyst (HESAC) composed of Fe, Co, Ni, and Ru metal atoms (FeCoNiRu-HESAC) is proposed. Negative formation energy and positive dissociation potentials indicate such materials' thermodynamic and electrochemical stability. Based on density functional theory (DFT) calculations, Co active sites lead to the overpotentials of 0.28 VRHE for oxygen evolution reaction (OER), 0.16 VRHE for hydrogen evolution reaction (HER), and 0.25 VRHE for CO2 reduction reaction (CO2RR) towards CO formation. These surpass the activity of CoN4 single-atom catalyst. More interestingly, the low CO2RR and HER overpotentials enable the FeCoNiRu-HESAC to produce syngas (CO + H2). In addition, the Fe, Ni, and Ru sites simply serve as counterparts to modify the performance of Co active sites through non-bonding interactions. Besides, machine learning (ML) implies that, the valence electrons of intermediates as well as the d orbital electrons of metal sites are the most important parameters affecting the reaction intermediates’ Gibbs free energy. According to these DFT and ML results, a strategy to design multifunctional HESACs electrocatalysts is developed.