A General Metal Ion Recognition Strategy to Mediate Dual-Atomic-Site Catalysts.

Heterogeneous dual-atomic-site catalysts (DACs) hold great potential for diverse applications. However, to date, the synthesis of DACs primarily relies on different atoms freely colliding on the support during synthesis, principally leading to low yields. Herein, we report a general metal ion recognition (MIR) strategy for constructing a series of DACs, including but not limited to Fe1Sn1, Fe1Co1, Fe1Ni1, Fe1Cu1, Fe1Mn1, Co1Ni1, Co1Cu1, Co2, and Cu2. This strategy is achieved by coupling target inorganometallic cations and anions as ion pairs, which are sequentially adsorbed onto a nitrogen-doped carbon substrate as the precursor. Taking the oxygen reduction reaction as an example, we demonstrated that the Fe1Sn1-DAC synthesized through this strategy delivers a record peak power density of 1.218 W cm-2 under 2.0 bar H2-O2 conditions and enhanced stability compared to the single-atom-site FeN4. Further study revealed that the superior performance arises from the synergistic effect of Fe1Sn1 dual vicinal sites, which effectively optimizes the adsorption of *OH and alleviates the troublesome Fenton-like reaction.

In Situ-Grown Ultrathin Catalyst Layers for Improving both Proton Exchange Membrane Fuel Cell and Anion Exchange Membrane Fuel Cell Performances.

The mass transport and ion conductivity in the catalyst layer are important for fuel cell performances. Here, we report an in situ-grown ultrathin catalyst layer (UTCL) to reduce the oxygen mass transport and a surface ionomer-coated gas diffusion layer method to reduce the ion conducting resistance. A significantly reduced catalyst layer thickness (ca. 1 µm) is achieved, and coupled with the ionomer introduction method, the ultrathin catalyst layer is in good contact with the membrane, resulting in high ion conductivity and high Pt utilization. This ultrathin catalyst layer is suitable for both proton exchange membrane fuel cells and anion exchange membrane fuel cells, giving peak power densities of 2.24 and 1.11 W cm-2, respectively, which represent an increase of more than 30% compared with the membrane electrode assembly (MEA) fabricated by using traditional Pt/C power catalysts. Electrochemical impedance spectra and limiting current tests demonstrate the reduced charge transfer, mass transfer, and ohmic resistances in the ultrathin catalyst layer membrane electrode assembly, resulting in the promoted fuel cell performances.

Unraveling the Influence of Nafion Content on the Performance of Proton-Exchange Membrane Fuel Cells from the Perspective of Triple-Phase Boundary.

By combining molecular simulations and experimental measurements, the effect of the Nafion content on the performance of proton-exchange membrane fuel cells (PEMFCs) is explained from the perspective of the triple-phase boundary (TPB). The evaporation process of Nafion solvent is simulated on a triple-phase model to mimic the formation of the TPB, and the influence of the Nafion content on the TPB structure is investigated. When the Nafion content is 1.415 mg/m2, the coverages of Nafion on both Pt particles and the carbon carrier are saturated at 42.1% and 32.7%, respectively. With the increase of Nafion content, the amount of water molecules around Pt particles is increased, and the surrounding O2 content is decreased. The experimental PEMFC performance has confirmed such simulation results, which demonstrates a trend of enhancing first and then weakening with the increase of Nafion content and reaches a maximum with the Nafion content of 2.96 mg/m2. Therefore, the correlation between the structure of the TPB and the cell's efficiency has been established at a molecular level, enabling enhancements in the design of the TPB morphology and an increase in PEMFC efficiency.

Direct Microenvironment Modulation of CO2 Electroreduction: Negatively Charged Ag Sites Going beyond Catalytic Surface Reactions.

Electrochemical reduction of CO2 is an important way to achieve carbon neutrality, and much effort has been devoted to the design of active sites. Apart from elevating the intrinsic activity, expanding the functionality of active sites may also boost catalytic performance. Here we designed "negatively charged Ag (nc-Ag)" active sites featuring both the intrinsic activity and the capability of regulating microenvironment, through modifying Ag nanoparticles with atomically dispersed Sn species. Different from conventional active sites (which only mediate the surface processes by bonding with the intermediates), the nc-Ag sites could also manipulate environmental species. Therefore, the sites could not only activate CO2, but also regulate interfacial H2O and CO2, as confirmed by operando spectroscopies. The catalyst delivers a high current density with a CO faradaic efficiency of 97 %. Our work here opens up new opportunities for the design of multifunctional electrocatalytic active sites.

Iridium-Based Alkaline Hydrogen Oxidation Reaction Electrocatalysts.

The hydroxide exchange membrane fuel cells (HEMFCs) are promising but lack of high-performance anode hydrogen oxidation reaction (HOR) electrocatalysts. The platinum group metals (PGMs) have the HOR activity in alkaline medium two to three orders of magnitude lower than those in acid, leading to the high required PGMs amount on anode to achieve high HEMFC performance. The mechanism study demonstrates the hydrogen binding energy of the catalyst determines the alkaline HOR kinetics, and the adsorbed OH and water on the catalyst surface promotes HOR. Iridium (Ir) has a unique advantage for alkaline HOR due to its similar hydrogen binding energy to Pt and enhanced adsorption of OH. However, the HOR activity of Ir/C is still unsatisfied in practical HEMFC applications. Further fine tuning the adsorption of the intermediate on Ir-based catalysts is of great significance to improve their alkaline HOR activity, which can be reasonably realized by structure design and composition regulation. In this concept, we address the current understanding about the alkaline HOR mechanism and summarize recent advances of Ir-based electrocatalysts with enhanced alkaline HOR activity. We also discuss the perspectives and challenges on Ir-based electrocatalysts in the future.

Atomically dispersed Iridium on Mo2C as an efficient and stable alkaline hydrogen oxidation reaction catalyst.

Hydroxide exchange membrane fuel cells (HEMFCs) have the advantages of using cost-effective materials, but hindered by the sluggish anodic hydrogen oxidation reaction (HOR) kinetics. Here, we report an atomically dispersed Ir on Mo2C nanoparticles supported on carbon (IrSA-Mo2C/C) as highly active and stable HOR catalysts. The specific exchange current density of IrSA-Mo2C/C is 4.1 mA cm-2ECSA, which is 10 times that of Ir/C. Negligible decay is observed after 30,000-cycle accelerated stability test. Theoretical calculations suggest the high HOR activity is attributed to the unique Mo2C substrate, which makes the Ir sites with optimized H binding and also provides enhanced OH binding sites. By using a low loading (0.05 mgIr cm-2) of IrSA-Mo2C/C as anode, the fabricated HEMFC can deliver a high peak power density of 1.64 W cm-2. This work illustrates that atomically dispersed precious metal on carbides may be a promising strategy for high performance HEMFCs.

An all-metallic nanovesicle for hydrogen oxidation.

Vesicle, a microscopic unit that encloses a volume with an ultrathin wall, is ubiquitous in biomaterials. However, it remains a huge challenge to create its inorganic metal-based artificial counterparts. Here, inspired by the formation of biological vesicles, we proposed a novel biomimetic strategy of curling the ultrathin nanosheets into nanovesicles, which was driven by the interfacial strain. Trapped by the interfacial strain between the initially formed substrate Rh layer and subsequently formed RhRu overlayer, the nanosheet begins to deform in order to release a certain amount of strain. Density functional theory (DFT) calculations reveal that the Ru atoms make the curling of nanosheets more favorable in thermodynamics applications. Owing to the unique vesicular structure, the RhRu nanovesicles/C displays excellent hydrogen oxidation reaction (HOR) activity and stability, which has been proven by both experiments and DFT calculations. Specifically, the HOR mass activity of RhRu nanovesicles/C are 7.52 A mg(Rh+Ru)-1 at an overpotential of 50 mV at the rotating disk electrode (RDE) level; this is 24.19 times that of commercial Pt/C (0.31 mA mgPt-1). Moreover, the hydroxide exchange membrane fuel cell (HEMFC) with RhRu nanovesicles/C displays a peak power density of 1.62 W cm-2 in the H2-O2 condition, much better than that of commercial Pt/C (1.18 W cm-2). This work creates a new biomimetic strategy to synthesize inorganic nanomaterials, paving a pathway for designing catalytic reactors.

Dilute RuCo Alloy Synergizing Single Ru and Co Atoms as Efficient and CO-Resistant Anode Catalyst for Anion Exchange Membrane Fuel Cells.

Ruthenium (Ru) is considered a promising candidate catalyst for alkaline hydroxide oxidation reaction (HOR) due to its hydrogen binding energy (HBE) like that of platinum (Pt) and its much higher oxygenophilicity than that of Pt. However, Ru still suffers from insufficient intrinsic activity and CO resistance, which hinders its widespread use in anion exchange membrane fuel cells (AEMFCs). Here, we report a hybrid catalyst (RuCo)NC+SAs/N-CNT consisting of dilute RuCo alloy nanoparticles and atomically single Ru and Co atoms on N-doped carbon nanotubes The catalyst exhibits a state-of-the-art activity with a high mass activity of 7.35 A mgRu -1. More importantly, when (RuCo)NC+SAs/N-CNT is used as an anode catalyst for AEMFCs, its peak power density reaches 1.98 W cm-2, which is one of the best AEMFCs properties of noble metal-based catalysts at present. Moreover, (RuCo)NC+SAs/N-CNT has superior long-time stability and CO resistance. The experimental and density functional theory (DFT) results demonstrate that the dilute alloying and monodecentralization of the exotic element Co greatly modulates the electronic structure of the host element Ru, thus optimizing the adsorption of H and OH and promoting the oxidation of CO on the catalyst surface, and then stimulates alkaline HOR activity and CO tolerance of the catalyst.

Enhancing H2O2 Electrosynthesis at Industrial-Relevant Current in Acidic Media on Diatomic Cobalt Sites.

Electrocatalytic synthesis of hydrogen peroxide (H2O2) in acidic media is an efficient and eco-friendly approach to produce inherently stable H2O2, but limited by the lack of selective and stable catalysts under industrial-relevant current densities. Herein, we report a diatomic cobalt catalyst for two-electron oxygen reduction to efficiently produce H2O2 at 50-400 mA cm-2 in acid. Electrode kinetics study shows a >95% selectivity for two-electron oxygen reduction on the diatomic cobalt sites. In a flow cell device, a record-high production rate of 11.72 mol gcat-1 h-1 and exceptional long-term stability (100 h) are realized under high current densities. In situ spectroscopic studies and theoretical calculations reveal that introducing a second metal into the coordination sphere of the cobalt site can optimize the binding strength of key H2O2 intermediates due to the downshifted d-band center of cobalt. We also demonstrate the feasibility of processing municipal plastic wastes through decentralized H2O2 production.

Dynamic chloride ion adsorption on single iridium atom boosts seawater oxidation catalysis.

Seawater electrolysis offers a renewable, scalable, and economic means for green hydrogen production. However, anode corrosion by Cl- pose great challenges for its commercialization. Herein, different from conventional catalysts designed to repel Cl- adsorption, we develop an atomic Ir catalyst on cobalt iron layered double hydroxide (Ir/CoFe-LDH) to tailor Cl- adsorption and modulate the electronic structure of the Ir active center, thereby establishing a unique Ir-OH/Cl coordination for alkaline seawater electrolysis. Operando characterizations and theoretical calculations unveil the pivotal role of this coordination state to lower OER activation energy by a factor of 1.93. The Ir/CoFe-LDH exhibits a remarkable oxygen evolution reaction activity (202 mV overpotential and TOF = 7.46 O2 s-1) in 6 M NaOH+2.8 M NaCl, superior over Cl--free 6 M NaOH electrolyte (236 mV overpotential and TOF = 1.05 O2 s-1), with 100% catalytic selectivity and stability at high current densities (400-800 mA cm-2) for more than 1,000 h.

Tuning the apparent hydrogen binding energy to achieve high-performance Ni-based hydrogen oxidation reaction catalyst.

High-performance platinum-group-metal-free alkaline hydrogen oxidation reaction catalysts are essential for the hydroxide exchange membrane fuel cells, which generally require high Pt loadings on the anode. Herein, we report a highly active hydrogen oxidation reaction catalyst, NiCuCr, indicated by the hydroxide exchange membrane fuel cell with a high peak power density of 577 mW cm-2 (18 times as high as the Ni/C anode) and a stability of more than 150 h (a degradation rate slower by 7 times than the Ni/C anode). The spectroscopies demonstrate that the alloy effect from Cu weakens the hydrogen binding, and the surface Cr2O3 species enhance the interfacial water binding. Both effects bring an optimized apparent hydrogen binding energy and thus lead to the high hydrogen oxidation reaction performance of NiCuCr. These results suggest that the apparent hydrogen binding energy determines the hydrogen oxidation reaction performance and that its tuning is beneficial toward high electrocatalytic performance.

Metal-support interaction boosts the stability of Ni-based electrocatalysts for alkaline hydrogen oxidation.

Ni-based hydrogen oxidation reaction (HOR) electrocatalysts are promising anode materials for the anion exchange membrane fuel cells (AEMFCs), but their application is hindered by their inherent instability for practical operations. Here, we report a TiO2 supported Ni4Mo (Ni4Mo/TiO2) catalyst that can effectively catalyze HOR in alkaline electrolyte with a mass activity of 10.1 ± 0.9 A g-1Ni and remain active even up to 1.2 V. The Ni4Mo/TiO2 anode AEMFC delivers a peak power density of 520 mW cm-2 and durability at 400 mA cm-2 for nearly 100 h. The origin for the enhanced activity and stability is attributed to the down-shifted d band center, caused by the efficient charge transfer from TiO2 to Ni. The modulated electronic structure weakens the binding strength of oxygen species, rendering a high stability. The Ni4Mo/TiO2 has achieved greatly improved stability both in half cell and single AEMFC tests, and made a step forward for feasibility of efficient and durable AEMFCs.

A replacement strategy for regulating local environment of single-atom Co-SxN4-x catalysts to facilitate CO2 electroreduction.

The performances of single-atom catalysts are governed by their local coordination environments. Here, a thermal replacement strategy is developed for the synthesis of single-atom catalysts with precisely controlled and adjustable local coordination environments. A series of Co-SxN4-x (x = 0, 1, 2, 3) single-atom catalysts are successfully synthesized by thermally replacing coordinated N with S at elevated temperature, and a volcano relationship between coordinations and catalytic performances toward electrochemical CO2 reduction is observed. The Co-S1N3 catalyst has the balanced COOH*and CO* bindings, and thus locates at the apex of the volcano with the highest performance toward electrochemical CO2 reduction to CO, with the maximum CO Faradaic efficiency of 98 ± 1.8% and high turnover frequency of 4564 h-1 at an overpotential of 410 mV tested in H-cell with CO2-saturated 0.5 M KHCO3, surpassing most of the reported single-atom catalysts. This work provides a rational approach to control the local coordination environment of the single-atom catalysts, which is important for further fine-tuning the catalytic performance.

Tuning Intermediates Adsorption and C─N Coupling for Efficient Urea Electrosynthesis Via Doping Ni into Cu.

Simultaneous electrochemical reduction of nitrite and carbon dioxide (CO2 ) under mild reaction conditions offers a new sustainable and low-cost approach for urea synthesis. However, the development of urea electrosynthesis thus far still suffers from low selectivity due to the high energy barrier of * CO formation and the subsequent C─N coupling. In this work, a highly active dendritic Cu99 Ni1 catalyst is developed to enable the highly selective electrosynthesis of urea from co-reduction of nitrite and CO2 , reaching a urea Faradaic efficiency (FE) and production rate of 39.8% and 655.4 µg h-1  cm-2 , respectively, at -0.7 V versus reversible hydrogen electrode (RHE). In situ Fourier-transform infrared spectroscopy (FT-IR) measurements together with density functional theory (DFT) calculations demonstrate that Ni doping into Cu can significantly enhance the adsorption energetics of the key reaction intermediates and facilitate the C─N coupling. This work not only provides a new strategy to design efficient electrocatalysts for urea synthesis but also offers deep insights into the mechanism of C─N coupling during the co-reduction of nitrite and CO2 .

Stabilizing ruthenium dioxide with cation-anchored sulfate for durable oxygen evolution in proton-exchange membrane water electrolyzers.

Ruthenium dioxide is the most promising alternative to the prevailing but expensive iridium-based catalysts for the oxygen evolution reaction in proton-exchange membrane water electrolyzers. However, the under-coordinated lattice oxygen of ruthenium dioxide is prone to over-oxidation, and oxygen vacancies are formed at high oxidation potentials under acidic corrosive conditions. Consequently, ruthenium atoms adjacent to oxygen vacancies are oxidized into soluble high-valence derivatives, causing the collapse of the ruthenium dioxide crystal structure and leading to its poor stability. Here, we report an oxyanion protection strategy to prevent the formation of oxygen vacancies on the ruthenium dioxide surface by forming coordination-saturated lattice oxygen. Combining density functional theory calculations, electrochemical measurements, and a suite of operando spectroscopies, we showcase that barium-anchored sulfate can greatly impede ruthenium loss and extend the lifetime of ruthenium-based catalysts during acidic oxygen evolution, while maintaining the activity. This work paves a new way for designing stable and active anode catalysts toward acidic water splitting.

Design of Superior Electrocatalysts for Proton-Exchange Membrane-Water Electrolyzers: Importance of Catalyst Stability and Evolution.

By virtue of the high energy conversion efficiency and compact facility, proton exchange membrane water electrolysis (PEMWE) is a promising green hydrogen production technology ready for commercial applications. However, catalyst stability is a challenging but often-ignored topic for the electrocatalyst design, which retards the device applications of many newly-developed electrocatalysts. By defining catalyst stability as the function of activity versus time, we ascribe the stability issue to the evolution of catalysts or catalyst layers during the water electrolysis. We trace the instability sources of electrocatalysts as the function versus time for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in acid and classify them into internal and external sources. Accordingly, we summarize the latest studies for stability improvements into five strategies, i. e., thermodynamic stable active site construction, precatalyst design, support regulation, superwetting electrode fabrication, and catalyst-ionomer interface engineering. With the help of ex-situ/ in-situ characterizations and theoretical calculations, an in-depth understanding of the instability sources benefits the rational development of highly active and stable HER/OER electrocatalysts for PEMWE applications.

p-Block Bismuth Nanoclusters Sites Activated by Atomically Dispersed Bismuth for Tandem Boosting Electrocatalytic Hydrogen Peroxide Production.

Constructing electrocatalysts with p-block elements is generally considered rather challenging owing to their closed d shells. Here for the first time, we present a p-block-element bismuth-based (Bi-based) catalyst with the co-existence of single-atomic Bi sites coordinated with oxygen (O) and sulfur (S) atoms and Bi nanoclusters (Biclu ) (collectively denoted as BiOSSA /Biclu ) for the highly selective oxygen reduction reaction (ORR) into hydrogen peroxide (H2 O2 ). As a result, BiOSSA /Biclu gives a high H2 O2 selectivity of 95 % in rotating ring-disk electrode, and a large current density of 36 mA cm-2 at 0.15 V vs. RHE, a considerable H2 O2 yield of 11.5 mg cm-2 h-1 with high H2 O2 Faraday efficiency of ∼90 % at 0.3 V vs. RHE and a long-term durability of ∼22 h in H-cell test. Interestingly, the experimental data on site poisoning and theoretical calculations both revealed that, for BiOSSA /Biclu , the catalytic active sites are on the Bi clusters, which are further activated by the atomically dispersed Bi coordinated with O and S atoms. This work demonstrates a new synergistic tandem strategy for advanced p-block-element Bi catalysts featuring atomic-level catalytic sites, and the great potential of rational material design for constructing highly active electrocatalysts based on p-block metals.

Interfacial assembly of binary atomic metal-Nx sites for high-performance energy devices.

Anion-exchange membrane fuel cells and Zn-air batteries based on non-Pt group metal catalysts typically suffer from sluggish cathodic oxygen reduction. Designing advanced catalyst architectures to improve the catalyst's oxygen reduction activity and boosting the accessible site density by increasing metal loading and site utilization are potential ways to achieve high device performances. Herein, we report an interfacial assembly strategy to achieve binary single-atomic Fe/Co-Nx with high mass loadings through constructing a nanocage structure and concentrating high-density accessible binary single-atomic Fe/Co-Nx sites in a porous shell. The prepared FeCo-NCH features metal loading with a single-atomic distribution as high as 7.9 wt% and an accessible site density of around 7.6 × 1019 sites g-1, surpassing most reported M-Nx catalysts. In anion exchange membrane fuel cells and zinc-air batteries, the FeCo-NCH material delivers peak power densities of 569.0 or 414.5 mW cm-2, 3.4 or 2.8 times higher than control devices assembled with FeCo-NC. These results suggest that the present strategy for promoting catalytic site utilization offers new possibilities for exploring efficient low-cost electrocatalysts to boost the performance of various energy devices.

Atomic-thick metastable phase RhMo nanosheets for hydrogen oxidation catalysis.

Metastable phase two-dimensional catalysts provide great flexibility for modifying their chemical, physical, and electronic properties. However, the synthesis of ultrathin metastable phase two-dimensional metallic nanomaterials is highly challenging, mainly due to the anisotropic nature of metallic materials and their thermodynamically unstable ground-state. Here, we report free-standing RhMo nanosheets with atomic thickness and a unique core/shell (metastable phase/stable phase) structure. The polymorphic interface between the core region and shell region stabilizes and activates metastable phase catalysts; the RhMo Nanosheets/C shows excellent hydrogen oxidation activity and stability. Specifically, the mass activities of RhMo Nanosheets/C is 6.96 A mgRh-1; this is 21.09 times higher than that of commercial Pt/C (0.33 A mgPt-1). Density functional theory calculations suggest that the interface aids in the dissociation of H2 and the H species can then spillover to weak H binding sites for desorption, providing excellent hydrogen oxidation activity for RhMo nanosheets. This work advances the highly controlled synthesis of two-dimensional metastable phase noble metals and provides great directions for the design of high-performance catalysts for fuel cells and beyond.

Revealing the Crystal Phase-Activity Relationship on NiRu Alloy Nanoparticles Encapsulated in N-Doped Carbon towards Efficient Hydrogen Evolution Reaction.

Adjusting the crystal phase of a metal alloy is an important method to optimize catalytic performance. However, detailed understanding about the phase-property relationship for the hydrogen evolution reaction (HER) is still limited. In this work, the crystal phase-activity relationship of NiRu nanoparticles is studied employing N-doped carbon shell coated NiRu nanoparticles with different phase contents. It is found that the NiRu@NC (mix) with both face-centred cubic (fcc) and thermodynamically unstable hexagonal close-packed (hcp) phase NiRu give the best HER performance. Further activity studies demonstrate that hcp NiRu has better HER performance, and NiRu@NC (mix) with rich (∼70 %) hcp phase presented outstanding performance with an overpotential of only 27 mV @ 10 mA ⋅ cm-2 . The high HER activity of NiRu@NC (mix) is attributed to the formation of hcp phase. This finding indicates that the regulation of crystal structure can provide a new strategy for optimizing HER activity.