Showing papers on "Overpotential published in 2022"
TL;DR: In this paper , a family of fluorinated-1,2-diethoxyethanes as electrolyte solvents were designed and synthesized, which achieved high conductivity, low and stable overpotential, >99.5% Li||Cu half-cell efficiency (up to 99.9%, ± 0.1% fluctuation) and fast activation (Li efficiency > 99.3% within two cycles).
Abstract: Electrolyte engineering improved cycling of Li metal batteries and anode-free cells at low current densities; however, high-rate capability and tuning of ionic conduction in electrolytes are desirable yet less-studied. Here, we design and synthesize a family of fluorinated-1,2-diethoxyethanes as electrolyte solvents. The position and amount of F atoms functionalized on 1,2-diethoxyethane were found to greatly affect electrolyte performance. Partially fluorinated, locally polar –CHF2 is identified as the optimal group rather than fully fluorinated –CF3 in common designs. Paired with 1.2 M lithium bis(fluorosulfonyl)imide, these developed single-salt-single-solvent electrolytes simultaneously enable high conductivity, low and stable overpotential, >99.5% Li||Cu half-cell efficiency (up to 99.9%, ±0.1% fluctuation) and fast activation (Li efficiency >99.3% within two cycles). Combined with high-voltage stability, these electrolytes achieve roughly 270 cycles in 50-μm-thin Li||high-loading-NMC811 full batteries and >140 cycles in fast-cycling Cu||microparticle-LiFePO4 industrial pouch cells under realistic testing conditions. The correlation of Li+–solvent coordination, solvation environments and battery performance is investigated to understand structure–property relationships. Cycling capability, especially at high rates, is limited for lithium metal batteries. Here the authors report electrolyte solvent design through fine-tuning of molecular structures to address the cyclability issue and unravel the electrolyte structure–property relationship for battery applications.
203 citations
TL;DR: In this paper , a family of fluorinated-1,2-diethoxyethanes as electrolyte solvents were designed and synthesized, which achieved high conductivity, low and stable overpotential, >99.5% Li||Cu half-cell efficiency (up to 99.9%, ± 0.1% fluctuation) and fast activation (Li efficiency > 99.3% within two cycles).
Abstract: Electrolyte engineering improved cycling of Li metal batteries and anode-free cells at low current densities; however, high-rate capability and tuning of ionic conduction in electrolytes are desirable yet less-studied. Here, we design and synthesize a family of fluorinated-1,2-diethoxyethanes as electrolyte solvents. The position and amount of F atoms functionalized on 1,2-diethoxyethane were found to greatly affect electrolyte performance. Partially fluorinated, locally polar –CHF2 is identified as the optimal group rather than fully fluorinated –CF3 in common designs. Paired with 1.2 M lithium bis(fluorosulfonyl)imide, these developed single-salt-single-solvent electrolytes simultaneously enable high conductivity, low and stable overpotential, >99.5% Li||Cu half-cell efficiency (up to 99.9%, ±0.1% fluctuation) and fast activation (Li efficiency >99.3% within two cycles). Combined with high-voltage stability, these electrolytes achieve roughly 270 cycles in 50-μm-thin Li||high-loading-NMC811 full batteries and >140 cycles in fast-cycling Cu||microparticle-LiFePO4 industrial pouch cells under realistic testing conditions. The correlation of Li+–solvent coordination, solvation environments and battery performance is investigated to understand structure–property relationships. Cycling capability, especially at high rates, is limited for lithium metal batteries. Here the authors report electrolyte solvent design through fine-tuning of molecular structures to address the cyclability issue and unravel the electrolyte structure–property relationship for battery applications.
193 citations
TL;DR: This work provides inspiration for optimizing the catalytic activity through combining crystalline and amorphous heterojunction, which can be implemented for other transition metal compound electrocatalysts.
Abstract: Amorphous and heterojunction materials have been widely used in the field of electrocatalytic hydrogen evolution due to their unique physicochemical properties. However, the current used individual strategy still has limited effects. Hence efficient tailoring tactics with synergistic effect are highly desired. Herein, the authors have realized the deep optimization of catalytic activity by a constructing crystalline–amorphous CoSe2/CoP heterojunction. Benefiting from the strong electronic coupling at the interfaces, the d‐band center of the material moves further down compared to its crystalline–crystalline counterpart, optimizing the valence state and the H adsorption of Co and lowering the kinetic barrier of hydrogen evolution reaction (HER). The heterojunction shows an overpotential of 65 mV to drive a current density of 10 mA cm−2 in the acidic medium. Besides, it also shows competitive properties in both neutral and basic media. This work provides inspiration for optimizing the catalytic activity through combining a crystalline and amorphous heterojunction, which can be implemented for other transition metal compound electrocatalysts.
156 citations
TL;DR: In this paper, the authors developed CoP-nitrogen-doped carbon@NiFeP nanoflakes (CoP-NC@NFP), derived from MOF enriched with multiple active sites for multifunctional water splitting and zinc-air battery applications.
150 citations
TL;DR: In this paper, a cotton-derived cellulose film was used as the separator for aqueous zinc-ion batteries (Zn-MnO2), which can effectively inhibit zinc dendrites and harmful side reactions.
138 citations
132 citations
TL;DR: In this article , a CoP-nitrogen-doped [email protected] nanoflakes was derived from MOF enriched with multiple active sites, and the experimental results revealed that the multiple active catalytic sites were responsible for the excellent charge transfer kinetics and electrocatalytic performance with respect to water splitting.
125 citations
TL;DR: In this article , the authors employed cotton-derived cellulose film prepared by a facile filtration method as the separator for aqueous zinc-ion batteries (AZIBs).
124 citations
TL;DR: In this paper , the authors reported that the benzoate anions-intercalated NiFe-layered double hydroxide nanosheet on carbon cloth (BZ-NiFe-LDH/CC) behaves as a highly efficient and durable monolithic catalyst for alkaline seawater oxidation, affords enlarged interlayer spacing of LDH, inhibits chlorine (electro)chemistry, and alleviates local pH drop of the electrode.
Abstract: Seawater electrolysis is an extremely attractive approach for harvesting clean hydrogen energy, but detrimental chlorine species (i.e., chloride and hypochlorite) cause severe corrosion at the anode. Here, we report our recent finding that benzoate anions-intercalated NiFe-layered double hydroxide nanosheet on carbon cloth (BZ-NiFe-LDH/CC) behaves as a highly efficient and durable monolithic catalyst for alkaline seawater oxidation, affords enlarged interlayer spacing of LDH, inhibits chlorine (electro)chemistry, and alleviates local pH drop of the electrode. It only needs an overpotential of 320 mV to reach a current density of 500 mA·cm–2 in 1 M KOH. In contrast to the fast activity decay of NiFe-LDH/CC counterpart during long-term electrolysis, BZ-NiFe-LDH/CC achieves stable 100-h electrolysis at an industrial-level current density of 500 mA·cm–2 in alkaline seawater. Operando Raman spectroscopy studies further identify structural changes of disordered δ (NiIII-O) during the seawater oxidation process.
117 citations
TL;DR: In this paper , a series of Ru nanocrystals from single atoms, subnanometric clusters to larger nanoparticles was synthesized, aiming at investigating the size-dependent activity of hydrogen evolution in alkaline media.
Abstract: Subnanometric metal clusters usually have unique electronic structures and may display electrocatalytic performance distinctive from single atoms (SAs) and larger nanoparticles (NPs). However, the electrocatalytic performance of clusters, especially the size-activity relationship at the sub-nanoscale, is largely unexplored. Here, we synthesize a series of Ru nanocrystals from single atoms, subnanometric clusters to larger nanoparticles, aiming at investigating the size-dependent activity of hydrogen evolution in alkaline media. It is found that the d band center of Ru downshifts in a nearly linear relationship with the increase of diameter, and the subnanometric Ru clusters with d band center closer to Femi level display a stronger water dissociation ability and thus superior hydrogen evolution activity than SAs and larger nanoparticles. Benefiting from the high metal utilization and strong water dissociation ability, the Ru clusters manifest an ultrahigh turnover frequency of 43.3 s-1 at the overpotential of 100 mV, 36.1-fold larger than the commercial Pt/C.
117 citations
TL;DR: In this paper, a hybrid nanocomposite (FeCo/FeCoP@NMn-CNS-800) was constructed by one-step pyrolysis of the metal precursors and polyinosinic acid.
TL;DR: In this article , the authors reported phosphated IrMo bimetallic clusters supported by macroporous nitrogen-doped carbon (IrMoP/MNC) as a highly efficient alkaline HER catalyst and demonstrated that P and Mo synergistically tune the electronic structure of atomically dispersed Ir to improve adsorption and desorption of the reactant H2O and the product OH−.
TL;DR: In this paper , the integration of Fe dopant and interfacial FeOOH into Ni-MOFs [Fe-doped-(Ni-MOF)/FeOOH] to construct Fe-ONi-O-Fe bonding is demonstrated and elucidate the origin of remarkable electrocatalytic performance.
Abstract: The integration of Fe dopant and interfacial FeOOH into Ni-MOFs [Fe-doped-(Ni-MOFs)/FeOOH] to construct Fe-O-Ni-O-Fe bonding is demonstrated and elucidate the origin of remarkable electrocatalytic performance of Ni-MOFs. X-ray absorption/photoelectron spectroscopy and theoretical calculation results indicate that Fe-O-Ni-O-Fe bonding can facilitate the distorted coordinated structure of Ni site with short nickel-oxygen bond and low coordination number, and can promote the redistribution of Ni/Fe charge density to efficiently regulate the adsorption behavior of key intermediates with near-optimal d-band center. Here the Fe-doped-(Ni-MOFs)/FeOOH with interfacial Fe-O-Ni-O-Fe bonding shows superior catalytic performance for OER with a low overpotential of 210 mV at 15 mA cm-2 and excellent stability with ~3% attenuation after 120 h cycle test. This study will provide a novel strategy to design high-performance Ni/Fe-based electrocatalysts for OER in alkaline media.
TL;DR: In this article , the authors report the use of hydrogen spillover-bridged water dissociation/hydrogen formation processes occurring at the synergistically hybridized Ni3S2/Cr2S3 sites to incapacitate the inhibition effect of high-current-density-induced high hydrogen coverage at the water Dissociation site and concurrently promote Volmer/Tafel processes.
Abstract: Water-alkaline electrolysis holds a great promise for industry-scale hydrogen production but is hindered by the lack of enabling hydrogen evolution reaction electrocatalysts to operate at ampere-level current densities under low overpotentials. Here, we report the use of hydrogen spillover-bridged water dissociation/hydrogen formation processes occurring at the synergistically hybridized Ni3S2/Cr2S3 sites to incapacitate the inhibition effect of high-current-density-induced high hydrogen coverage at the water dissociation site and concurrently promote Volmer/Tafel processes. The mechanistic insights critically important to enable ampere-level current density operation are depicted from the experimental and theoretical studies. The Volmer process is drastically boosted by the strong H2O adsorption at Cr5c sites of Cr2S3, the efficient H2O* dissociation via a heterolytic cleavage process (Cr5c-H2O* + S3c(#) → Cr5c-OH* + S3c-H#) on the Cr5c/S3c sites in Cr2S3, and the rapid desorption of OH* from Cr5c sites of Cr2S3 via a new water-assisted desorption mechanism (Cr5c-OH* + H2O(aq) → Cr5c-H2O* + OH-(aq)), while the efficient Tafel process is achieved through hydrogen spillover to rapidly transfer H# from the synergistically located H-rich site (Cr2S3) to the H-deficient site (Ni3S2) with excellent hydrogen formation activity. As a result, the hybridized Ni3S2/Cr2S3 electrocatalyst can readily achieve a current density of 3.5 A cm-2 under an overpotential of 251 ± 3 mV in 1.0 M KOH electrolyte. The concept exemplified in this work provides a useful means to address the shortfalls of ampere-level current-density-tolerant Hydrogen evolution reaction (HER) electrocatalysts.
TL;DR: In this article , the authors introduce the peculiarities of Te element, summarize Te doping and the extraordinary performance of its compounds in OER, with emphasis on the scientific mechanism behind Te element promoting the OER kinetic process.
Abstract: In the 21st century, the rapid development of human society has made people's demand for green energy more and more urgent. The high-energy-density hydrogen energy obtained by fully splitting water is not only environmentally friendly, but also is expected to solve the problems caused by the intermittent nature of new energy. However, the slow kinetics and large overpotential of the oxygen evolution reaction (OER) limit its application. The introduction of Te element is expected to bring new breakthroughs. With the least electronegativity among the chalcogens, the Te element has many special properties, such as multivalent states, strong covalentity, and high electrical conductivity, which make it a promising candidate in electrocatalytic OER. In this review, we introduce the peculiarities of Te element, summarize Te doping and the extraordinary performance of its compounds in OER, with emphasis on the scientific mechanism behind Te element promoting the OER kinetic process. Finally, challenges and development prospects of the applications of Te element in OER are presented.
TL;DR: The FeCo/FeCoP@NMn-CNS-800-assembled rechargeable Zn-air battery presented an open-circuit voltage of 1.522 V (vs. RHE), a peak power density of 135.0 mW cm-2, and long-term durability by charge-discharge cycling for 200 h, surpassing commercial Pt/C + RuO2 based counterpart as mentioned in this paper .
TL;DR: In this paper , electron-abundant Ir/Rh sites, as highly active centers for the hydrogen evolution reaction (HER), are realized by fabricating Ir1−xRhxSb alloys through the arc melting method.
Abstract: Alloying noble metals with non‐noble metals is a promising method to fabricate catalysts, with the advantages of reduced noble metal usage and excellent activity. In this work, electron‐abundant Ir/Rh sites, as highly active centers for the hydrogen evolution reaction (HER), are realized by fabricating Ir1−xRhxSb alloys through the arc‐melting method. The electron transfer from Sb to Ir/Rh makes the latter negatively charged, leading to considerably optimized adsorption for active H species during HER. As a result, the Ir1−xRhxSb alloy exhibits outstanding activity for HER, with an optimized overpotential of 22 mV at 10 mA cm–2 and a Tafel slope of 47.6 mV dec–1. This work provides insights into highly active alloys and sheds light on the utilization of electron‐abundant metal atoms.
TL;DR: In this paper , the OER active sites for three mainstream types of NPMCs including non-precious transition metal oxides/(oxy)hydroxides, metal-free carbon materials, and hybrid nonprecious metal and carbon composites are reviewed.
Abstract: The oxygen evolution reaction (OER) generally exists in electrochemistry‐enabled applications that are coupled with cathodic reactions like hydrogen evolution, carbon dioxide reduction, ammonia synthesis, and electrocatalytic hydrogenation. The OER heavily impacts the overall energy efficiency of these devices because the sluggish OER kinetics result in a huge overpotential, thus, a large amount of efficient catalysts are needed. The benchmark iridium and ruthenium (Ir/Ru)‐based materials (mostly used in acid media) are, however, significantly limited by their scarcity. Non‐precious metal‐based catalysts (NPMCs) have emerged as the most promising alternatives; however, they tend to degrade quickly under the harsh operating conditions of typical OER devices. Another challenge is the unsatisfying performance of OER catalysts when integrated in real‐world devices. Herein, the OER active sites for three mainstream types of NPMCs including non‐precious transition metal oxides/(oxy)hydroxides, metal‐free carbon materials, and hybrid non‐precious metal and carbon composites are reviewed. In addition, possible degradation mechanisms for active sites and mitigation strategies are discussed in detail. This review also provides insights into the gaps between R&D of NPMCs for the OER and their applications in practical devices.
TL;DR: In this article , an atomically dispersed Ru/Co dual-sites catalyst is reported anchored on N-doped carbon (Ru/Co-N-C) for outstanding oxygen evolution reaction (OER) and hydrogen evolution reaction in both acidic and alkaline electrolytes.
Abstract: The development of bifunctional water‐splitting electrocatalysts that are efficient and stable over a wide range of pH is of great significance but challenging. Here, an atomically dispersed Ru/Co dual‐sites catalyst is reported anchored on N‐doped carbon (Ru/Co–N–C) for outstanding oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in both acidic and alkaline electrolytes. The Ru/Co–N–C catalyst requires the overpotential of only 13 and 23 mV for HER, 232 and 247 mV for OER to deliver a current density of 10 mA cmgeo−2 in 0.5 m H2SO4 and 1 m KOH, respectively, outperforming benchmark catalysts Pt/C and RuO2. Theoretical calculations reveal that the introduction of Co–N4 sites into Ru/Co–N–C efficiently modify the electronic structure of Ru by enlarging Ru–O covalency and increasing Ru electron density, which in turn optimize the bonding strength between oxygen/hydrogen intermediate species with Ru sites, thereby enhancing OER and HER performance. Furthermore, the incorporation of Co–N4 sites induces electron redistribution around Ru–N4, thus enhancing corrosion–resistance of Ru/Co–N–C during acid and alkaline electrolysis. The Ru/Co–N–C has been applied in a proton exchange membrane water electrolyzer and steady operation is demonstrated at a high current density of 450 mA cmgeo−2 for 330 h.
TL;DR: In this paper , the authors concluded the latest developments of bimetallic phosphides for a series of photocatalytic reactions and proposed the current development prospects and prospective challenges in many ways of BMPs.
TL;DR: Li2O nanoparticles suspended in liquid electrolytes were investigated as a proof of concept in this article , where the role played by Li2O in the liquid electrolyte and solid-electrolyte interphases of the Li anode were elucidated.
Abstract: Designing a stable solid-electrolyte interphase on a Li anode is imperative to developing reliable Li metal batteries. Herein, we report a suspension electrolyte design that modifies the Li+ solvation environment in liquid electrolytes and creates inorganic-rich solid-electrolyte interphases on Li. Li2O nanoparticles suspended in liquid electrolytes were investigated as a proof of concept. Through theoretical and empirical analyses of Li2O suspension electrolytes, the roles played by Li2O in the liquid electrolyte and solid-electrolyte interphases of the Li anode are elucidated. Also, the suspension electrolyte design is applied in conventional and state-of-the-art high-performance electrolytes to demonstrate its applicability. Based on electrochemical analyses, improved Coulombic efficiency (up to ~99.7%), reduced Li nucleation overpotential, stabilized Li interphases and prolonged cycle life of anode-free cells (~70 cycles at 80% of initial capacity) were achieved with the suspension electrolytes. We expect this design principle and our findings to be expanded into developing electrolytes and solid-electrolyte interphases for Li metal batteries.
TL;DR: In this article , a non-concentrated aqueous zinc trifluoromethanesulfonate (Zn(OTF)2) electrolyte with 1,2-dimethoxyethane (DME) additive is used to simultaneously regulate the electrolyte structure and Zn interface chemistry.
TL;DR: In this paper , an as-synthesized P-doped NiMoO4/MoO2 heterostructure nanorods exhibit an extraordinary low overpotential of −23 mV at a current density of 10 mA cm−2, which is highly comparable to the performance of the state-of-theart Pt/C coated on nickel foam (NF) catalyst.
TL;DR: In this paper , a way to regulate the local spin state and band structure simultaneously in Ni3S2 nanosheets was proposed to balance the adsorption of the two active species.
Abstract: The separate modulation of the adsorption of *O and *OOH is challenging in oxygen evolution reaction (OER), which results in a large overpotential and slow kinetics. To balance the adsorption of the two active species, here, a way to regulate the local spin state and band structure simultaneously in Ni3S2 nanosheets is reported. The adequate doping of W heteroatoms causes the electron depletion from the Ni active site, which modulates the spin state of eg electrons, weakening the adsorption of *O. Additionally, the introduction of S vacancies contributes to the upshift of the d band center, which strengthens the adsorption of *OOH. In this manner, the adsorption of Ni3S2 for the active intermediates is optimized, resulting in a considerably improved overpotential of 246 mV at 100 mA cm−2 and a Tafel slope of 66 mV dec−1. This work provides insights into the exploration of OER catalysts through synergistic modulation of the spin state and the band structure.
TL;DR: In this article , a series of metal hydroxide-organic frameworks (MHOFs) synthesized by transforming layered hydroxides into two-dimensional sheets crosslinked using aromatic carboxylate linkers is presented.
Abstract: The oxygen evolution reaction is central to making chemicals and energy carriers using electrons. Combining the great tunability of enzymatic systems with known oxide-based catalysts can create breakthrough opportunities to achieve both high activity and stability. Here we report a series of metal hydroxide–organic frameworks (MHOFs) synthesized by transforming layered hydroxides into two-dimensional sheets crosslinked using aromatic carboxylate linkers. MHOFs act as a tunable catalytic platform for the oxygen evolution reaction, where the π–π interactions between adjacent stacked linkers dictate stability, while the nature of transition metals in the hydroxides modulates catalytic activity. Substituting Ni-based MHOFs with acidic cations or electron-withdrawing linkers enhances oxygen evolution reaction activity by over three orders of magnitude per metal site, with Fe substitution achieving a mass activity of 80 A \({\rm{g}}_{\rm{catalyst}}^{-1}\) at 0.3 V overpotential for 20 h. Density functional theory calculations correlate the enhanced oxygen evolution reaction activity with the MHOF-based modulation of Ni redox and the optimized binding of oxygenated intermediates.
TL;DR: In this article, Co9S8 nanoclusters implanted in Co/Mn-S,S,N multi-doped porous carbon are fabricated with the mixture of Eriochrome black T (EBT), metal precursors and dicyandiamide by a coordination regulated pyrolysis strategy.
TL;DR: In this article , a high-performance catalysts with high electrocatalytic performance for oxygen evolution reaction (OER) at the industrial grade current density of 500 mA cm−2 and fast reaction kinetics with a small Tafel slope of 32 mV dec−1 were fabricated.
Abstract: Designing and fabricating well-defined heterointerface catalysts with high electrocatalytic performance for oxygen evolution reaction (OER) at the industrial grade current density still remains a huge challenge. Here the flower-like nanosheets with rich Fe2O3/NiFe-layered double hydroxides (LDHs) heterointerfaces were fabricated, and they exhibit superior catalytic activity with a very low overpotential of 220 mV for OER at the industrial grade current density of 500 mA cm− 2 and fast reaction kinetics with a small Tafel slope of 32 mV dec−1. Based on the analyses of operando Raman spectra, DFT theoretical calculations and electrochemical characterizations, the superior electrocatalytic performance of catalysts for OER at the industrial grade current density can be attributed to Fe2O3/NiFe-LDHs heterointerfaces that can obviously promote interfacial electron transfer from Ni2+ to Fe3+ and optimize d-orbit electronic configuration with eg occupancy of Ni close to the unity, resulting in moderate adsorption/desorption energies of oxygenated intermediates, and thus facilitating remarkably electrocatalytic performance and superior intrinsic kinetics for OER in alkaline media.
TL;DR: In this article , a 3D multifunctional host consisting of N−doped carbon fibers embedded with Cu nanoboxes (denoted as Cu NBs@NCFs) is rationally designed and developed for stable ZMAs.
Abstract: The practical application of Zn‐metal anodes (ZMAs) is mainly impeded by the limited lifespan and low Coulombic efficiency (CE) resulting from the Zn dendrite growth and side reactions. Herein, a 3D multifunctional host consisting of N‐doped carbon fibers embedded with Cu nanoboxes (denoted as Cu NBs@NCFs) is rationally designed and developed for stable ZMAs. The 3D macroporous configuration and hollow structure can lower the local current density and alleviate the large volume change during the repeated cycling processes. Furthermore, zincophilic Cu and in‐situ‐formed Cu–Zn alloy can act as homogeneous nucleation sites to minimize the Zn nucleation overpotential, further guiding uniform and dense Zn deposition. As a result, this Cu NBs@NCFs host exhibits high CE of Zn plating/stripping for 1000 cycles. The Cu NBs@NCFs–Zn electrode shows low voltage hysteresis and prolonged cycling life (450 h) with dendrite‐free behaviors. As a proof‐of‐concept demonstration, a Zn‐ion full cell is fabricated based on this Cu NBs@NCFs–Zn anode, which demonstrates decent rate capability and improved cycling performance.
TL;DR: In this article, a Co-metal-organic framework (MOF) derived cobalt diselenide laminated with a transition metal dichalcogenide (TMSD) was used to develop a bifunctional electrocatalyst for water splitting.
TL;DR: In this article , a new range of high entropy alloy (HEA) self-supported electrodes with uniform HEA nanoparticles grown on carbon cloth was experimentally prepared for glycerol oxidation reaction.
Abstract: Electrochemical glycerol oxidation reaction (GOR) is an attractive alternative anodic reaction to oxygen evolution reaction for a variety of electrolytic synthesis, thanks to the possibility of mass production of glycerol from biomass and the relative low thermodynamic potential of GOR. The development of high-activity cheap electrocatalysts toward GOR yet faces a daunting challenge. Herein, we experimentally prepare a new range of high entropy alloy (HEA) self-supported electrodes with uniform HEA nanoparticles grown on carbon cloth. The systematic electrochemical studies verify that the HEA-CoNiCuMnMo electrode exhibits attractive performance for GOR electrocatalysis with low overpotential and high selectivity toward formate products. The surface atomic configurations of HEA-CoNiCuMnMo are studied by a self-developed machine learning-based Monte Carlo simulation, which points out the catalytic active center to be Mo sites coordinated by Mn, Mo, and Ni. We further develop a hybrid alkali/acid flow electrolytic cell by pairing alkaline GOR with acidic hydrogen evolution reaction using the HEA-CoNiCuMnMo and the commercial RhIr/Ti as the anode and the cathode, respectively, which only requires an applied voltage of 0.55 V to reach an electrolytic current density of 10 mA cm-2 and maintains long-term electrolysis stability over 12 days continuous running at 50 mA cm-2 with Faraday efficiencies of over 99% for H2 in the cathode and 92% for formate production in the anode.