Integrating Host Design and Tailored Electronic Effects of Yolk-Shell Zn-Mn Diatomic Sites for Efficient CO2 Electroreduction.

Modulating the surface and spatial structure of the host is associated with the reactivity of the active site, and also enhances the mass transfer effect of the CO2 electroreduction process (CO2 RR). Herein, we describe the development of two-step ligand etch-pyrolysis to access an asymmetric dual-atomic-site catalyst (DASC) composed of a yolk-shell carbon framework (Zn1 Mn1 -SNC) derived from S,N-coordinated Zn-Mn dimers anchored on a metal-organic framework (MOF). In Zn1 Mn1 -SNC, the electronic effects of the S/N-Zn-Mn-S/N configuration are tailored by strong interactions between Zn-Mn dual sites and co-coordination with S/N atoms, rendering structural stability and atomic distribution. In an H-cell, the Zn1 Mn1 -SNC DASC shows a low onset overpotential of 50 mV and high CO Faraday efficiency of 97 % with a low applied overpotential of 343 mV, thus outperforming counterparts, and in a flow cell, it also reaches a high current density of 500 mA cm-2 at -0.85 V, benefitting from the high structure accessibility and active dual sites. DFT simulations showed that the S,N-coordinated Zn-Mn diatomic site with optimal adsorption strength of COOH* lowers the reaction energy barrier, thus boosting the intrinsic CO2 RR activity on DASC. The structure-property correlation found in this study suggests new ideas for the development of highly accessible atomic catalysts.

Establishing a Robust Nonlinear Targeted Switch for C1 Electroproduction in Atomic Alloy Cox/Pd Bimetallenes.

Establishing a targeted switch for CO2 conversion under electric drive is essential for achieving carbon-balance by enabling selective chemicals. However, engineering the topological assembly of active sites to precisely regulate the competing pathways for various intermediates has been plagued by unclear structure-function relationships. To tailor the CO/formate pathways, herein we established a robust nonlinear targeted switch with tunable active Cox sites integrated into Pd metallene, which involves Co1/Pd single-atom alloy (favoring CO) and Co2/Pd diatomic alloy (favoring formate). Transitioning from Co1/Pd to Co2/Pd atomic alloy bimetallenes resulted in a nonlinear, high-contrast flip in selectivity, surpassing 94% for CO and formate productions in both H-cell and flow cell. Furthermore, the superior selectivity and current efficiency for CO (> 80 %) and formate (> 88%) were consistently maintained at -150 mA cm-2 over continuous 200 h. Theoretical simulations and in-situ spectroscopy analyses unveiled that appropriate adjacent metal site combinations (Pd-Pd, Pd-Co and Co-Co) lead to tunable dz2 band center and a nonlinear shift in preferred adsorption configurations of intermediates, dictating the C1 pathways. Our finding reveals a desired switch in C1 selectivity and robust stability within Cox/Pd system, providing a new perspective for fine-tuning energy conversion processes through specific topological assembly.

Selective Activation of Lattice Oxygen Site Through Coordination Engineering to Boost the Activity and Stability of Oxygen Evolution Reaction.

Although Ru-based materials are among the outstanding catalysts for the oxygen evolution reaction (OER), the instability issue still haunts them and impedes the widespread application. The instability of Ru-based OER catalysts is generally ascribed to the formation of soluble species through the over-oxidation of Ru and structural decomposition caused by involvement of lattice oxygen. Herein, an effective strategy of selectively activating the lattice oxygen around Ru site is proposed to improve the OER activity and stability. Our synthesized spinel-type electrocatalyst of Ru and Zn co-doped Co3O4 showed an ultralow overpotential of 172 mV at 10 mA cm-2 and a long-term stability reaching to 100 hours at 10 mA cm-2 for alkaline OER. The experimental results and theoretical simulations demonstrated that the lattice oxygen site jointly connected with the octahedral Ru and tetrahedral Zn atoms became more active than other oxygen sites near Ru atom, which further lowered the reaction energy barriers and avoided generating excessive oxygen vacancies to enhance the structural stability of Ru sites. The findings hope to provide a new perspective to improve the catalytic activity of Ru-incorporated OER catalysts and the stability of lattice-oxygen-mediated mechanism.

Pt Atomic Layers with Tensile Strain and Rich Defects Boost Ethanol Electrooxidation.

Surface and strain engineering are two effective strategies to improve performance; however, synergetic controls of surface and strain effects remains a grand challenge. Herein, we report a highly efficient and stable electrocatalyst with defect-rich Pt atomic layers coating an ordered Pt3Sn intermetallic core. Pt atomic layers enable the generation of 4.4% tensile strain along the [001] direction. Benefiting from synergetic controls of surface and strain engineering, Pt atomic-layer catalyst (Ptatomic-layer) achieves a remarkable enhancement on ethanol electrooxidation performance with excellent specific activity of 5.83 mA cm-2 and mass activity of 1166.6 mA mg Pt-1, which is 10.6 and 3.6 times higher than the commercial Pt/C, respectively. Moreover, the intermetallic core endows Ptatomic-layer with outstanding durability. In situ infrared reflection-absorption spectroscopy as well as density functional theory calculations reveal that tensile strain and rich defects of Ptatomci-layer facilitate to break C-C bond for complete ethanol oxidation for enhanced performance.

Isolated Ni Atoms Dispersed on Ru Nanosheets: High-Performance Electrocatalysts toward Hydrogen Oxidation Reaction.

Designing low-cost, high-efficiency, platinum-free electrocatalysts for the hydrogen oxidation reaction (HOR) in an alkaline electrolyte is of great importance for the development of anion exchange membrane fuel cells. Herein, we report a novel HOR catalyst, RuNi1, in which Ni is atomically dispersed on the Ru nanocrystals. To note, the as-prepared RuNi1 catalyst exhibits excellent catalytic activity and stability for HOR in alkaline media, which is superior to those of Ru-Ni bimetallic nanocrystals, pristine Ru, and commercial Pt/C catalysts. Density functional theory (DFT) calculations suggest that isolation of Ni atoms on Ru nanocrystals not only optimizes the hydrogen-binding energy but also decreases the free energy of water formation, thus leading to excellent electrocatalytic activity of RuNi1 catalyst. The results show that engineering a catalyst at an atomic level is highly effective for rational design of electrocatalysts with high performance.

Engineering Isolated Mn-N2C2 Atomic Interface Sites for Efficient Bifunctional Oxygen Reduction and Evolution Reaction.

Oxygen-involved electrochemical reactions are crucial for plenty of energy conversion techniques. Herein, we rationally designed a carbon-based Mn-N2C2 bifunctional electrocatalyst. It exhibits a half-wave potential of 0.915 V versus reversible hydrogen electrode for oxygen reduction reaction (ORR), and the overpotential is 350 mV at 10 mA cm-2 during oxygen evolution reaction (OER) in alkaline condition. Furthermore, by means of operando X-ray absorption fine structure measurements, we reveal that the bond-length-extended Mn2+-N2C2 atomic interface sites act as active centers during the ORR process, while the bond-length-shortened high-valence Mn4+-N2C2 moieties serve as the catalytic sites for OER, which is consistent with the density functional theory results. The atomic and electronic synergistic effects for the isolated Mn sites and the carbon support play a critical role to promote the oxygen-involved catalytic performance, by regulating the reaction free energy of intermediate adsorption. Our results give an atomic interface strategy for nonprecious bifunctional single-atom electrocatalysts.

In Situ Phosphatizing of Triphenylphosphine Encapsulated within Metal-Organic Frameworks to Design Atomic Co1-P1N3 Interfacial Structure for Promoting Catalytic Performance.

The engineering coordination environment offers great opportunity in performance tunability of isolated metal single-atom catalysts. For the most popular metal-Nx (MNx) structure, the replacement of N atoms by some other atoms with relatively weak electronegativity has been regarded as a promising strategy for optimizing the coordination environment of an active metal center and promoting its catalytic performance, which is still a challenge. Herein, we proposed a new synthetic strategy of an in situ phosphatizing of triphenylphosphine encapsulated within metal-organic frameworks for designing atomic Co1-P1N3 interfacial structure, where a cobalt single atom is costabilized by one P atom and three N atoms (denoted as Co-SA/P-in situ). In the acidic media, the Co-SA/P-in situ catalyst with Co1-P1N3 interfacial structure exhibits excellent activity and durability for the hydrogen evolution reaction (HER) with a low overpotential of 98 mV at 10 mA cm-2 and a small Tafel slope of 47 mV dec-1, which are greatly superior to those of catalyst with Co1-N4 interfacial structure. We discover that the bond-length-extended high-valence Co1-P1N3 atomic interface structure plays a crucial role in boosting the HER performance, which is supported by in situ X-ray absorption fine structure (XAFS) measurements and density functional theory (DFT) calculation. We hope this work will promote the development of high performance metal single-atom catalysts.

Design of a Single-Atom Indiumδ+ -N4 Interface for Efficient Electroreduction of CO2 to Formate.

Main-group element indium (In) is a promising electrocatalyst which triggers CO2 reduction to formate, while the high overpotential and low Faradaic efficiency (FE) hinder its practical application. Herein, we rationally design a new In single-atom catalyst containing exclusive isolated Inδ+ -N4 atomic interface sites for CO2 electroreduction to formate with high efficiency. This catalyst exhibits an extremely large turnover frequency (TOF) up to 12500 h-1 at -0.95 V versus the reversible hydrogen electrode (RHE), with a FE for formate of 96 % and current density of 8.87 mA cm-2 at low potential of -0.65 V versus RHE. Our findings present a feasible strategy for the accurate regulation of main-group indium catalysts for CO2 reduction at atomic scale.

Phase-Controlled Synthesis of Nickel Phosphide Nanocrystals and Their Electrocatalytic Performance for the Hydrogen Evolution Reaction.

The phase of nanocrystals has a key role in the modulation of catalytic properties. Uniform and well-crystallized nickel phosphide nanocrystals with controlled phases (Ni5 P4 , Ni2 P, and Ni12 P5 ) and narrow size distributions are synthesized by a wet chemical method. The phases of the as-synthesized nickel phosphide nanocrystals are controlled by the P/Ni precursor molar ratio, heating process, and time of reaction. Rarely reported nearly monodisperse 5.6 nm Ni5 P4 nanocrystals are successfully synthesized and show superior hydrogen evolution reaction (HER) activity. Only a low overpotential of 103 mV is required to achieve the HER current of 10 mA cm-2 at a low catalyst loading of 0.12 mg cm-2 . The high HER activity is attributed to the high quality of the as-obtained Ni5 P4 nanocrystals, which have the electronic effect from the Ni5 P4 phase and also high surface area owing to the small particle size. A systematic study of the controlled synthesis of nickel phosphide nanocrystals is shown in this paper, and the HER catalytic activity is improved through the phase- and size-controlled synthesis of nanocrystals.

Self-Assembly Precursor-Derived MoP Supported on N,P-Codoped Reduced Graphene Oxides as Efficient Catalysts for Hydrogen Evolution Reaction.

The design and synthesis of high-activity earth-abundant material-based electrocatalysts for hydrogen evolution reaction (HER) are of great significance. Here we develop a novel method to prepare a MoP nanoparticle supported on N,P-codoped reduced graphene oxides (MoP/N,P-rGO) by pyrolysis of the self-assembled precursor. Benefiting from the selected components of the assembly, P and N atoms are mixed at the molecular level, which leads to MoP nanoparticles uniformly attaching to the graphene substrate and a certain amount of N and P atoms codoping to graphene. The obtained MoP/N,P-rGO exhibits a good HER performance that only needs an overpotential of 115 mV to achieve a HER current density of 10 mA cm-2. The enhanced HER performance is due to the well-dispersed MoP nanoparticles and the synergistic effect from the doped graphene substrate. It shows that the selected functional components integrated by the self-assembly process are appropriate precursors for the synthesis of high-quality HER electrocatalysts.

Rational Control of the Selectivity of a Ruthenium Catalyst for Hydrogenation of 4-Nitrostyrene by Strain Regulation.

Tuning the selectivity of metal catalysts is of paramount importance yet a great challenge. A new strategy to effectively control the selectivity of metal catalysts, by tuning the lattice strain, is reported. A certain amount of Co atoms is introduced into Ru catalysts to compress the Ru lattice, as confirmed by aberration-corrected high-resolution transmission electron microscopy (HRTEM) and X-ray absorption fine structure (XAFS) measurements. We discover that the lattice strain of Ru catalysts can greatly affect their selectivity, and Ru with 3 % lattice compression exhibits extremely high catalytic selectivity for hydrogenation of 4-nitrostyrene to 4-aminostyrene compared to pristine Ru (99 % vs. 66 %). Theoretical studies confirm that the optimized lateral compressive strain facilitates hydrogenation of the nitro group but impedes the hydrogenation of the vinyl group. This study provides a new guideline for designing metal catalysts with high selectivity.

Rational Design of Single Molybdenum Atoms Anchored on N-Doped Carbon for Effective Hydrogen Evolution Reaction.

The highly efficient electrochemical hydrogen evolution reaction (HER) provides a promising pathway to resolve energy and environment problems. An electrocatalyst was designed with single Mo atoms (Mo-SAs) supported on N-doped carbon having outstanding HER performance. The structure of the catalyst was probed by aberration-corrected scanning transmission electron microscopy (AC-STEM) and X-ray absorption fine structure (XAFS) spectroscopy, indicating the formation of Mo-SAs anchored with one nitrogen atom and two carbon atoms (Mo1 N1 C2 ). Importantly, the Mo1 N1 C2 catalyst displayed much more excellent activity compared with Mo2 C and MoN, and better stability than commercial Pt/C. Density functional theory (DFT) calculation revealed that the unique structure of Mo1 N1 C2 moiety played a crucial effect to improve the HER performance. This work opens up new opportunities for the preparation and application of highly active and stable Mo-based HER catalysts.

Isolated Ni-atom catalyst supported on Ti3C2Tx with an asymmetrical C-Ni-N structure for the hydrogen evolution reaction.

Single-atom catalysts (SACs), distinguished by their exceptional atomic efficiency and modifiable coordination structures, find wide-ranging applicability, notably in the context of the hydrogen evolution reaction (HER). Herein, we synthesized a Ti3C2Tx-based Ni single-atom catalyst (Ni SA@N-Ti3C2Tx) by immersing a single Ni atom into the Ti vacancies of Ti3C2Tx and using a N-doping strategy. X-Ray adsorption fine structure revealed the formation of local Ni-N1C1 and an unsaturated C-Ni-N bridge configuration for isolated Ni species. Moreover, Ni SA@N-Ti3C2Tx exhibited an excellent HER performance with an overpotential of 63 mV at 10 mV cm-2. This work could enable use of MXene-based SACs in the HER.

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.

Artificial neural network for deciphering the structural transformation of condensed ZnO by extended x-ray absorption fine structure spectroscopy.

Pressure-induced structural phase transitions play a pivotal role in unlocking novel material functionalities and facilitating innovations in materials science. Nonetheless, unveiling the mechanisms of densification, which relies heavily on precise and comprehensive structural analysis, remains a challenge. Herein, we investigated the archetypalB4 →B1 phase transition pathway in ZnO by combining x-ray absorption fine structure (XAFS) spectroscopy with machine learning. Specifically, we developed an artificial neural network (NN) to decipher the extended-XAFS spectra by reconstructing the partial radial distribution functions of Zn-O/Zn pairs. This provided us with access to the evolution of the structural statistics for all the coordination shells in condensed ZnO, enabling us to accurately track the changes in the internal structural parameteruand the anharmonic effect. We observed a clear decrease inuand an increased anharmonicity near the onset of theB4 →B1 phase transition, indicating a preference for the iT phase as the intermediate state to initiate the phase transition that can arise from the softening of shear phonon modes. This study suggests that NN-based approach can facilitate a more comprehensive and efficient interpretation of XAFS under complexin-situconditions, which paves the way for highly automated data processing pipelines for high-throughput and real-time characterizations in next-generation synchrotron photon sources.

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.

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.

Electronic Metal-Support Interactions between Copper Nanoparticles and Nitrogen-Doped Ti3C2Tx MXene to Boost Peroxidase-like Activity for Detecting Astaxanthin.

Nanozymes with high activity and stability have emerged as a potential alternative to natural enzymes in the past years, but the relationship between the electronic metal-support interactions (EMSI) and catalytic performance in nanozymes still remains unclear. Herein, a copper nanoparticle nanozyme supported on N-doped Ti3C2Tx (Cu NPs@N-Ti3C2Tx) is successfully synthesized and the modulation of EMSI is achieved by introducing N species. The stronger EMSI between Cu NPs and Ti3C2Tx, involving electronic transfer and an interface effect, is revealed by X-ray photoelectron spectroscopy, soft X-ray absorption spectroscopy, and hard X-ray absorption fine spectroscopy at the atomic level. Consequently, Cu NPs@N-Ti3C2Tx nanozyme exhibits remarkable peroxidase-like activity, surpassing its counterpart (Cu NPs, Ti3C2Tx, Cu NPs-Ti3C2Tx), suggesting that EMSI significantly enhances catalytic performance. Benefiting from the excellent performance, the colorimetric platform based on Cu NPs@N-Ti3C2Tx nanozyme for detecting astaxanthin is constructed and shows a wide linear detection range of 0.01-50 µM and a limit of detection of 0.015 µM in the sunscreens. Density functional theory is further conducted to reveal that the excellent performance is ascribed to the stronger EMSI. This work opens an avenue for studying the influence of EMSI toward catalytic performance of nanozyme.

PtNi-W/C with Atomically Dispersed Tungsten Sites Toward Boosted ORR in Proton Exchange Membrane Fuel Cell Devices.

The performance of proton exchange membrane fuel cells is heavily dependent on the microstructure of electrode catalyst especially at low catalyst loadings. This work shows a hybrid electrocatalyst consisting of PtNi-W alloy nanocrystals loaded on carbon surface with atomically dispersed W sites by a two-step straightforward method. Single-atomic W can be found on the carbon surface, which can form protonic acid sites and establish an extended proton transport network at the catalyst surface. When implemented in membrane electrode assembly as cathode at ultra-low loading of 0.05 mgPt cm-2, the peak power density of the cell is enhanced by 64.4% compared to that with the commercial Pt/C catalyst. The theoretical calculation suggests that the single-atomic W possesses a favorable energetics toward the formation of *OOH whereby the intermediates can be efficiently converted and further reduced to water, revealing a interfacial cascade catalysis facilitated by the single-atomic W. This work highlights a novel functional hybrid electrocatalyst design from the atomic level that enables to solve the bottle-neck issues at device level.

Continuous electroproduction of formate via CO2 reduction on local symmetry-broken single-atom catalysts.

Atomic-level coordination engineering is an efficient strategy for tuning the catalytic performance of single-atom catalysts (SACs). However, their rational design has so far been plagued by the lack of a universal correlation between the coordination symmetry and catalytic properties. Herein, we synthesised planar-symmetry-broken CuN3 (PSB-CuN3) SACs through microwave heating for electrocatalytic CO2 reduction. Remarkably, the as-prepared catalysts exhibited a selectivity of 94.3% towards formate at -0.73 V vs. RHE, surpassing the symmetrical CuN4 catalyst (72.4% at -0.93 V vs. RHE). In a flow cell equipped with a PSB-CuN3 electrode, over 90% formate selectivity was maintained at an average current density of 94.4 mA cm-2 during 100 h operation. By combining definitive structural identification with operando X-ray spectroscopy and theoretical calculations, we revealed that the intrinsic local symmetry breaking from planar D4h configuration induces an unconventional dsp hybridisation, and thus a strong correlation between the catalytic activity and microenvironment of metal centre (i.e., coordination number and distortion), with high preference for formate production in CuN3 moiety. The finding opens an avenue for designing efficient SACs with specific local symmetries for selective electrocatalysis.