Locally Ordered Single-Atom Catalysts for Electrocatalysis

Single-atom catalysts manifest nearly 100 % atom utilization efficiency, well-defined active sites, and high selectivity. However, their practical applications are hindered by a low atom loading density, uncontrollable location, and ambiguous interaction with the support, thereby posing challenges to maximizing their electrocatalytic performance. To address these limitations, the ability to arrange randomly dispersed single atoms into locally ordered single-atom catalysts (LO-SACs) substantially influences the electronic effect between reactive sites and the support, the synergistic interaction among neighboring single atoms, the bonding energy of intermediates with reactive sites and the complexity of the mechanism. As such, it dramatically promotes reaction kinetics, reduces the energy barrier of the reaction, improves the performance of the catalyst and simplifies the reaction mechanism. In this review, firstly, we introduce a variety of compelling characteristics of LO-SACs as electrocatalysts. Subsequently, the synthetic strategies, characterization methods and applications of LO-SACs in electrocatalysis are discussed. Finally, the future opportunities and challenges are elaborated to encourage further exploration in this rapidly evolving field.     

Stabilizing Low-Valence Single Atoms by Constructing Metalloid Tungsten Carbide Supports for Efficient Hydrogen Oxidation and Evolution

Designing novel single-atom catalysts (SACs) supports to modulate the electronic structure is crucial to optimize the catalytic activity, but rather challenging. Herein, a general strategy is proposed to utilize the metalloid properties of supports to trap and stabilize single-atoms with low-valence states. A series of single-atoms supported on the surface of tungsten carbide (M-WC_x, M=Ru, Ir, Pd) are rationally developed through a facile pyrolysis method. Benefiting from the metalloid properties of WC_x, the single-atoms exhibit weak coordination with surface W and C atoms, resulting in the formation of low-valence active centers similar to metals. The unique metal-metal interaction effectively stabilizes the low-valence single atoms on the WC_x surface and improves the electronic orbital energy level distribution of the active sites. As expected, the representative Ru-WC_x exhibits superior mass activities of 7.84 and 62.52 A mg_Ru⁻¹ for the hydrogen oxidation and evolution reactions (HOR/HER), respectively. In-depth mechanistic analysis demonstrates that an ideal dual-sites cooperative mechanism achieves a suitable adsorption balance of H_ad and OH_ad, resulting in an energetically favorable Volmer step. This work offers new guidance for the precise construction of highly active SACs.     

Air-Stable Mn doped CuCl/CuO Hybrid Triquetrous Nanoarrays as Bifunctional Electrocatalysts for Overall Water Splitting

The development of highly efficient non-precious metal catalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is key for large-scale hydrogen evolution through water splitting technology. Here, we report an air-stable Cu-based nanostructure consisting of Mn doped CuCl and CuO (CuCl/CuO(Mn)-NF) as a dual functional electrocatalyst for water splitting. CuCl is identified as the main active component, together with Mn doping and the synergistic effect between CuCl and CuO are found to make responsibility for the excellent OER and HER catalytic activity and stability. The assembled electrolyzes also exhibit decent water splitting performance. This work not only provides a simple method for preparing Cu-based composite catalyst, but also demonstrates the great potential of Cu-based non-noble metal electrocatalysts for water splitting and other renewable energy conversion technologies.     

Designed Single Atom Bifunctional Electrocatalysts for Overall Water Splitting: 3d Transition Metal Atoms Doped Borophene Nanosheets

Single atom catalysts (SAC) for water splitting hold the promise of producing H₂ in a highly efficient and economical way. As the performance of SACs depends on the interaction between the adsorbate atom and supporting substrate, developing more efficient SACs with suitable substrates is of significance. In this work, inspired by the successful fabrications of borophene in experiments, we systematically study the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) activities of a series of 3d transition metal-based SACs supported by various borophene monolayers (BMs=α_sheet, α₁_sheet, and β₁_sheet borophene), TM/BMs, using density functional theory calculations and kinetic simulations. All of the TM/BMs systems exhibit superior HER performance compared to Pt with close to zero thermoneutral Gibbs free energy (ΔG_H*) of H adsorption. Furthermore, three Ni-deposited systems, namely, Ni/α_BM, Ni/α₁_BM and Ni/β₁_BM, were identified to be superior OER catalysts with remarkably reduced overpotentials. Based on these results, Ni/BMs can be expected to serve as stunning bifunctional electrocatalysts for water splitting. This work provides a guideline for developing efficient bifunctional electrocatalysts.     

Molecular Recognition Regulates Coordination Structure of Single-Atom Sites

Coordination engineering for single-atom sites has drawn increasing attention, yet its chemical synthesis remains a tough issue, especially for tailorable coordination structures. Herein, a molecular recognition strategy is proposed to fabricate single-atom sites with regulable local coordination structures. Specifically, a heteroatom-containing ligand serves as the guest molecule to induce coordination interaction with the metal-containing host, precisely settling the heteroatoms into the local structure of single-atom sites. As a proof of concept, thiophene is selected as the guest molecule, and sulfur atoms are successfully introduced into the local coordination structure of iron single-atom sites. Ultrahigh oxygen reduction electrocatalytic activity is achieved with a half-wave potential of 0.93 V versus reversible hydrogen electrode. Furthermore, the strategy possesses excellent universality towards diversified types of single-atom sites. This work makes breakthroughs in the fabrication of single-atom sites and affords new opportunities in structural regulation at the atomic level.     

Ir Nanoparticles Anchored on Metal-Organic Frameworks for Efficient Overall Water Splitting under pH-Universal Conditions

The construction of high-activity and low-cost electrocatalysts is critical for efficient hydrogen production by water electrolysis. Herein, we developed an advanced electrocatalyst by anchoring well-dispersed Ir nanoparticles on nickel metal-organic framework (MOF) Ni-NDC (NDC: 2,6-naphthalenedicarboxylic) nanosheets. Benefiting from the strong synergy between Ir and MOF through interfacial Ni−O−Ir bonds, the synthesized Ir@Ni-NDC showed exceptional electrocatalytic performance for hydrogen evolution reaction (HER), oxygen evolution reaction (OER) and overall water splitting in a wide pH range, superior to commercial benchmarks and most reported electrocatalysts. Theoretical calculations revealed that the charge redistribution of Ni−O−Ir bridge induced the optimization of H₂O, OH* and H* adsorption, thus leading to the accelerated electrochemical kinetics for HER and OER. This work provides a new clue to exploit bifunctional electrocatalysts for pH-universal overall water splitting.     

Electronic Perturbation of Copper Single-Atom CO2 Reduction Catalysts in a Molecular Way

Fine-tuning electronic structures of single-atom catalysts (SACs) plays a crucial role in harnessing their catalytic activities, yet challenges remain at a molecular scale in a controlled fashion. By tailoring the structure of graphdiyne (GDY) with electron-withdrawing/-donating groups, we show herein the electronic perturbation of Cu single-atom CO₂ reduction catalysts in a molecular way. The elaborately introduced functional groups (−F, −H and −OMe) can regulate the valance state of Cu^δ+, which is found to be directly scaled with the selectivity of the electrochemical CO₂-to-CH₄ conversion. An optimum CH₄ Faradaic efficiency of 72.3 % was achieved over the Cu SAC on the F-substituted GDY. In situ spectroscopic studies and theoretical calculations revealed that the positive Cu^δ+ centers adjusted by the electron-withdrawing group decrease the pK_a of adsorbed H₂O, promoting the hydrogenation of intermediates toward the CH₄ production. Our strategy paves the way for precise electronic perturbation of SACs toward efficient electrocatalysis.     

Bioinspired Single-Atom Sites Enable Efficient Oxygen Activation for Switching Anodic/Cathodic Electrochemiluminescence

Exploring advanced co-reaction accelerators with superior oxygen reduction activity that generate rich reactive oxygen species (ROS) has attracted great attention in boosting luminol-O₂ electrochemiluminescence (ECL). However, tuning accelerators for efficient and selective catalytic O₂ activation to switch anodic/cathodic ECL is very challenging. Herein, we report that enzyme-inspired Fe-based single-atom catalysts with axial N/C coordination structures (FeN₅, FeN₄© SACs) can generate specific ROS for cathodic/anodic ECL conversion. Mechanistic studies reveal that FeN₅ sites prefer to produce highly active hydroxyl radicals and afford direct cathodic luminescence by promoting the cleavage of O−O bonds through N-induced electron redistribution. In contrast, FeN₄© sites tend to produce superoxide radicals, resulting in inefficient anodic ECL. Benefiting from the enhanced cathodic ECL, FeN₅ SAC-based immunosensor was constructed for the sensitive detection of cancer biomarkers.     

Continuous Modulation of Electrocatalytic Oxygen Reduction Activities of Single-Atom Catalysts through p-n Junction Rectification

Fine-tuning single-atom catalysts (SACs) to surpass their activity limit remains challenging at their atomic scale. Herein, we exploit p-type semiconducting character of SACs having a metal center coordinated to nitrogen donors (MeN_x) and rectify their local charge density by an n-type semiconductor support. With iron phthalocyanine (FePc) as a model SAC, introducing an n-type gallium monosulfide that features a low work function generates a space-charged region across the junction interface, and causes distortion of the FeN₄ moiety and spin-state transition in the Fe^II center. This catalyst shows an over two-fold higher specific oxygen-reduction activity than that of pristine FePc. We further employ three other n-type metal chalcogenides of varying work function as supports, and discover a linear correlation between the activities of the supported FeN₄ and the rectification degrees, which clearly indicates that SACs can be continuously tuned by this rectification strategy.     

Atomically Dispersed Zn-Pyrrolic-N4 Cathode Catalysts for Hydrogen Fuel Cells

To achieve practical application of fuel cell, it is vital to develop highly efficient and durable Pt-free catalysts. Herein, we prepare atomically dispersed ZnNC catalysts with Zn-Pyrrolic-N₄ moieties and abundant mesoporous structure. The ZnNC-based anion-exchange membrane fuel cell (AEMFC) presents an ultrahigh peak power density of 1.63 and 0.83 W cm⁻² in H₂-O₂ and H₂-air (CO₂-free), and also exhibits long-term stability with more than 120 and 100 h for H₂-air (CO₂-free) and H₂-O₂, respectively. Density functional calculations further unveil that the Zn-Pyrrolic-N₄ structure is the origin of high activity of as-synthesized ZnNC catalyst, while the Zn-Pyridinic-N₄ moiety is inactive for oxygen reduction reaction (ORR), which successfully explain the puzzle why most Zn-metal-organic framework -derived ZnNC catalysts in previous reports did not present good ORR activity because of their Zn-Pyridinic-N₄ moieties. This work offers a new route for speeding up development of AEMFCs.     

Electrothermal Water-Gas Shift Reaction at Room Temperature with a Silicomolybdate-Based Palladium Single-Atom Catalyst

The water-gas shift (WGS) reaction is often conducted at elevated temperature and requires energy-intensive separation of hydrogen (H₂) from methane (CH₄), carbon dioxide (CO₂), and residual carbon monoxide (CO). Designing processes to decouple CO oxidation and H₂ production provides an alternative strategy to obtain high-purity H₂ streams. We report an electrothermal WGS process combining thermal oxidation of CO on a silicomolybdic acid (SMA)-supported Pd single-atom catalyst (Pd₁/CsSMA) and electrocatalytic H₂ evolution. The two half-reactions are coupled through phosphomolybdic acid (PMA) as a redox mediator at a moderate anodic potential of 0.6 V (versus Ag/AgCl). Under optimized conditions, our catalyst exhibited a TOF of 1.2 s⁻¹ with turnover numbers above 40 000 mol mol_Pd⁻¹ achieving stable H₂ production with a purity consistently exceeding 99.99 %.     

Atomically Dispersed FeN2P2 Motif with High Activity and Stability for Oxygen Reduction Reaction Over the Entire pH Range

The past decade has witnessed the great potential of Fe-based single-atom electrocatalysis in catalyzing oxygen reduction reaction (ORR). However, it remains a grand challenge to substantially improve their intrinsic activity and long-term stability in acidic electrolytes. Herein, we report a facile chemical vapor deposition strategy, by which high-density Fe atoms (3.97 wt%) are coordinated with square-planar para-positioned nitrogen and phosphorus atoms in a hierarchical carbon framework. The as-crafted atomically dispersed Fe catalyst (denoted Fe-SA/PNC) manifests an outstanding activity towards ORR over the entire pH range. Specifically, the half-wave potential of 0.92 V, 0.83 V, and 0.86 V vs. reversible hydrogen electrode (RHE) are attained in alkaline, neutral, and acidic electrolytes, respectively, representing the high performance among reported catalysts to date. Furthermore, after 30,000 durability cycles, the Fe-SA/PNC remains to be stable with no visible performance decay when tested in 0.1 M KOH and 0.5 M H₂SO₄, and only a minor negative shift of 40 mV detected in 0.1 M HClO₄, significantly outperforming commercial Pt/C counterpart. The coordination motif of Fe-SA/PNC is validated by density functional theory (DFT) calculations. This work provides atomic-level insight into improving the activity and stability of non-noble metal ORR catalysts, opening up an avenue to craft the desired single-atom electrocatalysts.     

Scalable Synthesis of Multi-Metal Electrocatalyst Powders and Electrodes and their Application for Oxygen Evolution and Water Splitting

Multi-metal electrocatalysts provide nearly unlimited catalytic possibilities arising from synergistic element interactions. We propose a polymer/metal precursor spraying technique that can easily be adapted to produce a large variety of compositional different multi-metal catalyst materials. To demonstrate this, 11 catalysts were synthesized, characterized, and investigated for the oxygen evolution reaction (OER). Further investigation of the most active OER catalyst, namely CoNiFeMoCr, revealed a polycrystalline structure, and operando Raman measurements indicate that multiple active sites are participating in the reaction. Moreover, Ni foam-supported CoNiFeMoCr electrodes were developed and applied for water splitting in flow-through electrolysis cells with electrolyte gaps and in zero-gap membrane electrode assembly (MEA) configurations. The proposed alkaline MEA-type electrolyzers reached up to 3 A cm⁻², and 24 h measurements demonstrated no loss of current density of 1 A cm⁻².     

Boosting Alkaline Hydrogen Evolution Reaction through Water Structure Manipulation

In the past, the design of efficient electrocatalyst materials for alkaline hydrogen evolution reaction (HER) was mostly focused on tuning the adsorption properties of reaction intermediates. A recent breakthrough shows that the performance can be improved by manipulating water structure at the electrode-electrolyte interface using atomically localized electric fields. The new approach was realized by using IrRu dizygotic single-atom sites and led to a significantly accelerated water dissociation and an overall improved alkaline HER performance. Supported by extensive data from advanced modeling, characterization, and electrochemical measurements, the work delivers an intricate examination of the interaction between water molecules and the catalyst surface, thereby enriching our understanding of water dissociation kinetics and offering new insights to boost overall alkaline HER efficiency.     

Construction of High-Density Binuclear Site Catalysts from Double Framework Interfaces at the Cooling Stage

Low-nuclear site catalysts with dual atoms have the potential for applications in energy and catalysis chemistry. Understanding the formation mechanism of dual metal sites is crucial for optimizing local structures and designing desired binuclear sites catalysts. In this study, we demonstrate for the first time the formation process of dual atoms through the pyrolysis of the interface of a double framework using Zn atoms in metal–organic frameworks and Co atoms in covalent organic frameworks. We unambiguously revealed that the cooling stage is the key point to form the binuclear sites by employing the in situ synchrotron radiation X-ray absorption spectrum technique. The binuclear site catalysts show higher activity and selectivity than single dispersed atom catalysts for electrocatalytic oxygen reduction. This work guides us to synthesize and optimize the various binuclear sites for extensive catalytic applications.     

High Valence State Sites as Favorable Reductive Centers for High-Current-Density Water Splitting

Electrochemical water splitting is a promising approach for producing sustainable and clean hydrogen. Typically, high valence state sites are favorable for oxidation evolution reaction (OER), while low valence states can facilitate hydrogen evolution reaction (HER). However, here we proposed a high valence state of Co³⁺ in Ni_9.5Co_0.5−S−FeO_x hybrid as the favorable center for efficient and stable HER, while structural analogues with low chemical states showed much worse performance. As a result, the Ni_9.5Co_0.5−S−FeO_x catalyst could drive alkaline HER with an ultra-low overpotential of 22 mV for 10 mA cm⁻², and 175 mV for 1000 mA cm⁻² at the industrial temperature of 60 °C, with an excellent stability over 300 h. Moreover, this material could work for both OER and HER, with a low cell voltage being 1.730 V to achieve 1000 mA cm⁻² for overall water splitting at 60 °C. X-ray absorption spectroscopy (XAS) clearly identified the high valence Co³⁺ sites, while in situ XAS during HER and theoretical calculations revealed the favorable electron capture at Co³⁺ and suitable H adsorption/desorption energy around Co³⁺, which could accelerate the HER. The understanding of high valence states to drive reductive reactions may pave the way for the rational design of energy-related catalysts.     

Dual-Atom Catalysts Derived from a Preorganized Covalent Organic Framework for Enhanced Electrochemical Oxygen Reduction

Dual-atom catalysts (DAC) are deemed as promising electrocatalysts due to the abundant active sites and adjustable electronic structure, but the fabrication of well-defined DAC is still full of challenges. Herein, bonded Fe dual-atom catalysts (Fe₂DAC) with Fe₂N₆C₈O₂ configuration were developed through one-step carbonization of a preorganized covalent organic framework with bimetallic Fe chelation sites (Fe₂COF). The transition from Fe₂COF to Fe₂DAC involved the dissociation of the nanoparticles and the capture of atoms by carbon defects. Benefitting from the optimized d-band center and enhanced adsorption of OOH* intermediates, Fe₂DAC exhibited outstanding oxygen reduction activity with a half-wave potential of 0.898 V vs. RHE. This work will guide more fabrication of dual-atom and even cluster catalysts from preorganized COF in the future.     

Activity And Stability of Single- And Di-Atom Catalysts for the O2 Reduction Reaction

Efficient and inexpensive catalysts for the O₂ reduction reaction (ORR) are needed for the advancement of renewable energy technologies. In this study, we designed a computational catalyst-screening method to identify single and di-atom metal dopants from first-row transition elements supported on defect-containing nitrogenated graphene surfaces for the ORR. Based on formation-energy calculations and micro-kinetic modelling of reaction pathways using intermediate binding free energies, we have identified four potentially interesting single-atom catalysts (SACs) and fifteen di-atom catalysts (DACs) with relatively high estimated catalytic activity at 0.8 V vs RHE. Among the best SACs, MnNC shows high stability in both acidic and alkaline media according to our model. For the DACs, we found four possible candidates, MnMn, FeFe, CoCo, and MnNi doped on quad-atom vacancy sites having considerable stability over a wide pH range. The remaining SACs and DACs with high activity are either less stable or show a stability region at an alkaline pH.     

Preparation of Hierarchical Cube‐on‐plate Metal Phosphides as Bifunctional Electrocatalysts for Overall Water Splitting

To rationally design efficient and cost‐effective electrocatalysts, a simple but efficient strategy has been developed to directly anchor prussian blue analogue (PBA) nanocubes on cobalt hydroxide nanoplates (PBA@Co(OH)₂) via the in‐situ interfacial precipitation process. Subsequently, the thermal treatment in the presence of sodium hydrogen phosphite enabled the successful transition into metal phosphides with the hierarchical cube‐on‐plate structure. When used as electrocatalytsts, the obtained bimetal phosphides exhibited good bifunctional electrocatalytic activities for hydrogen and oxygen evolution reactions with good long‐term stability. Thus, an enhanced performance for overall water splitting can be achieved, which could be ascribed to the hierarchical structure and favorable composition of as‐prepared bimetal phosphide for rapid electron and mass transfer. The present study demonstrates a favorable approach to modulate the composition and structure of metal phosphide for enhancing the electrocatalytic ability toward water splitting.     

A BiVO4 Photoanode with a VOx Layer Bearing Oxygen Vacancies Offers Improved Charge Transfer and Oxygen Evolution Kinetics in Photoelectrochemical Water Splitting

Sluggish oxygen evolution kinetics are one of the key limitations of bismuth vanadate (BiVO₄) photoanodes for efficient photoelectrochemical (PEC) water splitting. To address this issue, we report a vanadium oxide (VO_x) with enriched oxygen vacancies conformally grown on BiVO₄ photoanodes by a simple photo-assisted electrodeposition process. The optimized BiVO₄/VO_x photoanode exhibits a photocurrent density of 6.29 mA cm⁻² at 1.23 V versus the reversible hydrogen electrode under AM 1.5 G illumination, which is ca. 385 % as high as that of its pristine counterpart. A high charge-transfer efficiency of 96 % is achieved and stable PEC water splitting is realized, with a photocurrent retention rate of 88.3 % upon 40 h of testing. The excellent PEC performance is attributed to the presence of oxygen vacancies in VO_x that forms undercoordinated sites, which strengthen the adsorption of water molecules onto the active sites and promote charge transfer during the oxygen evolution reaction. This work demonstrates the potential of vanadium-based catalysts for PEC water oxidation.