PdMo bimetallene for oxygen reduction catalysis.

The efficient interconversion of chemicals and electricity through electrocatalytic processes is central to many renewable-energy initiatives. The sluggish kinetics of the oxygen reduction reaction (ORR) and the oxygen evolution reaction (OER)1-4 has long posed one of the biggest challenges in this field, and electrocatalysts based on expensive platinum-group metals are often required to improve the activity and durability of these reactions. The use of alloying5-7, surface strain8-11 and optimized coordination environments12 has resulted in platinum-based nanocrystals that enable very high ORR activities in acidic media; however, improving the activity of this reaction in alkaline environments remains challenging because of the difficulty in achieving optimized oxygen binding strength on platinum-group metals in the presence of hydroxide. Here we show that PdMo bimetallene-a palladium-molybdenum alloy in the form of a highly curved and sub-nanometre-thick metal nanosheet-is an efficient and stable electrocatalyst for the ORR and the OER in alkaline electrolytes, and shows promising performance as a cathode in Zn-air and Li-air batteries. The thin-sheet structure of PdMo bimetallene enables a large electrochemically active surface area (138.7 square metres per gram of palladium) as well as high atomic utilization, resulting in a mass activity towards the ORR of 16.37 amperes per milligram of palladium at 0.9 volts versus the reversible hydrogen electrode in alkaline electrolytes. This mass activity is 78 times and 327 times higher than those of commercial Pt/C and Pd/C catalysts, respectively, and shows little decay after 30,000 potential cycles. Density functional theory calculations reveal that the alloying effect, the strain effect due to the curved geometry, and the quantum size effect due to the thinness of the sheets tune the electronic structure of the system for optimized oxygen binding. Given the properties and the structure-activity relationships of PdMo metallene, we suggest that other metallene materials could show great promise in energy electrocatalysis.

Au/Pt Bimetallic Nanowires with Stepped Pt Sites for Enhanced C-C Cleavage in C2+ Alcohol Electro-oxidation Reactions.

Efficient C-C bond cleavage and oxidation of alcohols to CO2 is the key to developing highly efficient alcohol fuel cells for renewable energy applications. In this work, we report the synthesis of core/shell Au/Pt nanowires (NWs) with stepped Pt clusters deposited along the ultrathin (2.3 nm) stepped Au NWs as an active catalyst to effectively oxidize alcohols to CO2. The catalytic oxidation reaction is dependent on the Au/Pt ratios, and the Au1.0/Pt0.2 NWs have the largest percentage (∼75%) of stepped Au/Pt sites and show the highest activity for ethanol electro-oxidation, reaching an unprecedented 196.9 A/mgPt (32.5 A/mgPt+Au). This NW catalyst is also active in catalyzing the oxidation of other primary alcohols, such as methanol, n-propanol, and ethylene glycol. In situ X-ray absorption spectroscopy and infrared spectroscopy are used to characterize the catalyst structure and to identify key reaction intermediates, providing concrete evidence that the synergy between the low-coordinated Pt sites and the stepped Au NWs is essential to catalyze the alcohol oxidation reaction, which is further supported by DFT calculations that the C-C bond cleavage is indeed enhanced on the undercoordinated Pt-Au surface. Our study provides important evidence that a core/shell structure with stepped core/shell sites is essential to enhance electrochemical oxidation of alcohols and will also be central to understanding electro-oxidation reactions and to the future development of highly efficient direct alcohol fuel cells for renewable energy applications.

Single-Atom Cr-N4 Sites with High Oxophilicity Interfaced with Pt Atomic Clusters for Practical Alkaline Hydrogen Evolution Catalysis.

Although dispersing Pt atomic clusters (ACs) on a conducting support is a promising way to minimize the Pt amount required in hydrogen evolution reaction (HER), the catalytic mass activity and durability of Pt ACs are often unsatisfactory for alkaline HER due to their unfavorable water dissociation and challenges in stabilizing them against agglomeration and detachment. Herein, we report a class of single-atom Cr-N4 sites with high oxophilicity interfaced with Pt ACs on mesoporous carbon for achieving a highly active and stable alkaline HER in an anion-exchange-membrane water electrolyzer (AEMWE). The as-made catalyst achieves the highest reported Pt mass activity (37.6 times higher than commercial Pt/C) and outstanding operational stability. Experimental and theoretical studies elucidate that the formation of a unique Pt-Cr quasi-covalent bonding interaction at the interface of Cr-N4 sites and Pt ACs effectively suppresses the migration and thermal vibration of Pt atoms to stabilize Pt ACs and contributes to the greatly enhanced catalytic stability. Moreover, oxophilic Cr-N4 sites adjacent to Pt ACs with favorable adsorption of hydroxyl species facilitate nearly barrierless water dissociation and thus enhance the HER activity. An AEMWE using this catalyst (with only 50 µgPt cm-2) can operate stably at an industrial-level current density of 500 mA cm-2 at 1.8 V for >100 h with a small degradation rate of 90 µV h-1.

S-Block Potassium Single-atom Electrocatalyst with K-N4 Configuration Derived from K+ /Polydopamine for Efficient Oxygen Reduction.

Currently, single-atom catalysts (SACs) research mainly focuses on transition metal atoms as active centers. Due to their delocalized s/p-bands, the s-block main group metal elements are typically regarded as catalytically inert. Herein, an s-block potassium SAC (K-N-C) with K-N4 configuration is reported for the first time, which exhibits excellent oxygen reduction reaction (ORR) activity and stability under alkaline conditions. Specifically, the half-wave potential (E1/2 ) is up to 0.908 V, and negligible changes in E1/2 are observed after 10,000 cycles. In addition, the K-N-C offers an exceptional power density of 158.1 mW cm-2 and remarkable durability up to 420 h in a Zn-air battery. Density functional theory (DFT) simulations show that K-N-C has bifunctional active K and C sites, can optimize the free energy of ORR reaction intermediates, and adjust the rate-determining steps. The crystal orbital Hamilton population (COHP) results showed that the s orbitals of K played a major role in the adsorption of intermediates, which was different from the d orbitals in transition metals. This work significantly guides the rational design and catalytic mechanism research of s-block SACs with high ORR activity.

Inducing Covalent Atomic Interaction in Intermetallic Pt Alloy Nanocatalysts for High-Performance Fuel Cells.

The harsh working environments of proton exchange membrane fuel cells (PEMFCs) pose huge challenges to the stability of Pt-based alloy catalysts. The widespread presence of metallic bonds with significantly delocalized electron distribution often lead to component segregation and rapid performance decay. Here we report L10 -Pt2 CuGa intermetallic nanoparticles with a unique covalent atomic interaction between Pt-Ga as high-performance PEMFC cathode catalysts. The L10 -Pt2 CuGa/C catalyst shows superb oxygen reduction reaction (ORR) activity and stability in fuel cell cathode (mass activity=0.57 A mgPt -1 at 0.9 V, peak power density=2.60/1.24 W cm-2 in H2 -O2 /air, 28 mV voltage loss at 0.8 A cm-2 after 30 000 cycles). Theoretical calculations reveal the optimized adsorption of oxygen intermediates via the formed biaxial strain on L10 -Pt2 CuGa surface, and the durability enhancement stems from the stronger Pt-M bonds than those in L11 -PtCu resulted from Pt-Ga covalent interactions.

Highly Surface-Distorted Pt Superstructures for Multifunctional Electrocatalysis.

Platinum (Pt) catalysts play a key role in energy conversion and storage processes, but the realization of further performance enhancement remains challenging. Herein, we report a new class of Pt superstructures (SSs) with surface distortion engineering by electrochemical leaching of PtTex SSs that can largely boost the oxygen reduction reaction (ORR), the methanol oxidation reaction (MOR), and the hydrogen evolution reaction (HER). In particular, the high-distortion (H)-Pt SSs achieve a mass activity of 2.24 A mg-1 at 0.90 VRHE for the ORR and 2.89 A mg-1 for the MOR as well as a low overpotential of 25.3 mV at 10 mA cm-2 for the HER. Moreover, the distorted surface features of Pt SSs can be preserved by mitigating the detrimental effects of agglomeration/degradation during long-time electrocatalysis. A multiscale modeling demonstrates that surface compressions, defects, and nanopores act in synergy for the enhanced ORR performance. This work highlights the advances of stable superstructure and distortion engineering for realizing high-performance Pt nanostructures.

Exclusive Strain Effect Boosts Overall Water Splitting in PdCu/Ir Core/Shell Nanocrystals.

Core/shell nanocatalysts are a class of promising materials, which achieve the enhanced catalytic activities through the synergy between ligand effect and strain effect. However, it has been challenging to disentangle the contributions from the two effects, which hinders the rational design of superior core/shell nanocatalysts. Herein, we report precise synthesis of PdCu/Ir core/shell nanocrystals, which can significantly boost oxygen evolution reaction (OER) via the exclusive strain effect. The heteroepitaxial coating of four Ir atomic layers onto PdCu nanoparticle gives a relatively thick Ir shell eliminating the ligand effect, but creates a compressive strain of ca. 3.60%. The strained PdCu/Ir catalysts can deliver a low OER overpotential and a high mass activity. Density functional theory (DFT) calculations reveal that the compressive strain in Ir shell downshifts the d-band center and weakens the binding of the intermediates, causing the enhanced OER activity. The compressive strain also boosts hydrogen evolution reaction (HER) activity and the strained nanocrystals can be served as excellent catalysts for both anode and cathode in overall water-splitting electrocatalysis.

Cu3N Nanocubes for Selective Electrochemical Reduction of CO2 to Ethylene.

Understanding the Cu-catalyzed electrochemical CO2 reduction reaction (CO2RR) under ambient conditions is both fundamentally interesting and technologically important for selective CO2RR to hydrocarbons. Current Cu catalysts studied for the CO2RR can show high activity but tend to yield a mixture of different hydrocarbons, posing a serious challenge on using any of these catalysts for selective CO2RR. Here, we report a new perovskite-type copper(I) nitride (Cu3N) nanocube (NC) catalyst for selective CO2RR. The 25 nm Cu3N NCs show high CO2RR selectivity and stability to ethylene (C2H4) at -1.6 V (vs reversible hydrogen electrode (RHE)) with the Faradaic efficiency of 60%, mass activity of 34 A/g, and C2H4/CH4 molar ratio of >2000. More detailed electrochemical characterization, X-ray photon spectroscopy, and density functional theory calculations suggest that the high CO2RR selectivity is likely a result of (100) Cu(I) stabilization by the Cu3N structure, which favors CO-CHO coupling on the (100) Cu3N surface, leading to selective formation of C2H4. Our study presents a good example of utilizing metal nitrides as highly efficient nanocatalysts for selective CO2RR to hydrocarbons that will be important for sustainable chemistry/energy applications.

Tungsten-Doped L10 -PtCo Ultrasmall Nanoparticles as a High-Performance Fuel Cell Cathode.

The commercialization of proton exchange membrane fuel cells (PEMFCs) relies on highly active and stable electrocatalysts for oxygen reduction reaction (ORR) in acid media. The most successful catalysts for this reaction are nanostructured Pt-alloy with a Pt-skin. The synthesis of ultrasmall and ordered L10 -PtCo nanoparticle ORR catalysts further doped with a few percent of metals (W, Ga, Zn) is reported. Compared to commercial Pt/C catalyst, the L10 -W-PtCo/C catalyst shows significant improvement in both initial activity and high-temperature stability. The L10 -W-PtCo/C catalyst achieves high activity and stability in the PEMFC after 50 000 voltage cycles at 80 °C, which is superior to the DOE 2020 targets. EXAFS analysis and density functional theory calculations reveal that W doping not only stabilizes the ordered intermetallic structure, but also tunes the Pt-Pt distances in such a way to optimize the binding energy between Pt and O intermediates on the surface.

Phase diagram, mechanical properties, and electronic structure of Nb-N compounds under pressure.

Niobium-nitrogen compounds, which are potential candidates for superhard multifunctional materials, may possess multiple stoichiometries and structures under pressure. Based on ab initio evolutionary structural searches, we predict three ground states (oP6-Nb2N, CW-NbN, and hP22-Nb5N6) and six stable high pressure phases (ε-NbN, AsNi-NbN, U2S3-Nb2N3, oC24-NbN2, mP8-NbN3, and mP20-NbN4) for Nb-N compounds at pressures up to 100 GPa. Among them, the oP6-Nb2N, oC24-NbN2, mP8-NbN3, and mP20-NbN4 have never been reported, and N-rich oC24-NbN2, mP8-NbN3, and mP20-NbN4 high pressure phases are recoverable to ambient pressure. We find that the structure of N-rich Nb-N compounds consists of NbNx polyhedral stacking configurations and connected with Nn (n = 2, 3, 4, and n) polymerizations, which can remarkably improve the elastic modulus. It is found that CW-NbN and mP20-NbN4 are two potential ultra-incompressible and hard materials with the hardness calculated to be 24.56 and 19.86 GPa, respectively, while other N-rich phases such as U2S3-Nb2N3, oC24-NbN2, and mP8-NbN3 are soft materials. Detailed electronic structure and chemical bonding analysis proved that the high hardness of CW-NbN and mP20-NbN4 stems from the strong covalent bonding and the fullfilled Nb-N bonding and antibonding states.

The low coordination number of nitrogen in hard tungsten nitrides: a first-principles study.

Tungsten-nitrogen (W-N) compounds are studied via a combination of first-principles calculations and variable-composition evolutionary structure searches. New candidate ground states and high-pressure phases at 3 : 2, 1 : 1, and 5 : 6 compositions are uncovered and established for possible synthesis. We found that the structures in 4/5-fold N coordination (i.e., NbO-WN and W5N6) are more favoured for the W-N system at low-pressures compared with the conventional 6-fold phases (rs-WN and δ-WN). We attribute the low N coordination feature of W-N ground states to the enhanced W 5d-N 2p orbital hybridization and strong covalent W-N bonding, which involves the full-filling of W-N bonding and antibonding states and can remarkably improve the mechanical strength and hardness. These findings not only clarify the phase diagram of the W-N system, but also shed light on the correlations of hardness with microscopic crystal and electronic structures.

Pressure-induced structural changes in NH4Br.

We report angle dispersive X-ray diffraction (XRD) measurements and Raman spectroscopy on NH4Br up to 70.0 GPa at room temperature. Three thermodynamically stable phases (phases II, IV, and V) are confirmed and a new possible phase (phase VI) of P21/m symmetry is proposed whose structure was established from Rietveld refinement of synchrotron XRD data for the first time. The phase sequence observed in NH4Br is in accordance with phase II → IV → V → VI. Phase V transforms into phase VI at about 57.8 GPa with a huge volume reduction of 30%. Still, the intramolecular distances are analyzed to better understand the nature of structures. The H-H interactions become markedly more important as the N-Br distances are compacted, which is probably the reason of the kink of symmetric stretching band (ν1) at the transition pressure.

High-pressure phase transition of MH3 (M: Er, Ho).

Motivated by the potential high temperature superconductivity in hydrogen-rich materials, high-pressure structures of ErH3 and HoH3 were studied by using genetic algorithm method. Our calculations indicate that both ErH3 and HoH3 transform from P-3c1 structure to a monoclinic C2/m structure at about 15 GPa, and then transforms into a cubic Fm-3m structure at about 40 GPa. ErH3 and HoH3 adopt the same P63/mmc structure with space group P63/mmc at above about 220 and 196 GPa, respectively. For ErH3, the P63/mmc phase is stable up to at least 300 GPa, while for HoH3, a phase transformation P63/mmc → Cmcm occurs at about 216 GPa, and the Cmcm phase is stable up to at least 300 GPa. The P-3c1 ErH3 and HoH3 are calculated to demonstrate non-metallic character, and the other phases are all metallic phases.

Experimental verification of the high pressure crystal structures in NH3BH3.

A detailed high-pressure study on NH3BH3 has been carried out using in situ synchrotron X-ray diffraction (XRD) and Raman scattering with a diamond anvil cell up to 20 and 33 GPa, respectively. The Rietveld refinement based on the XRD pattern and analysis of Raman data indicate two first-order phase transitions from the ambient pressure I4 mm structure (α-NH3BH3) to a high pressure Cmc21 phase (ß-NH3BH3) at 2.14 GPa, and further into a monoclinic P21 (Z = 2) phase (γ-NH3BH3) at 9.67 GPa. Fitting the measured volumetric compression data to the third order Birch-Murnaghan equation of state reveals a bulk modulus of B0 = 9.9 ± 0.5 and 17.0 ± 3.0 GPa (with fixed B0 (') = 4) for the ß-NH3BH3 below and above 5 GPa, respectively. Still, with the splitting of the NBH rock mode in Raman experiment, it is concluded that a second-order isostructural phase transition occurs at 5 GPa. By analyzing the dihydrogen bonding framework, the origin of the isostructural phase transition is attributed to the number of dihydrogen bondings per molecule in the Cmc21 phase increasing from 12 to 14 at 5 GPa.

Nonbonding Metal-Metal Interaction in Metal-Nitrogen-Carbon Single-Atom Catalysts Boosts CO Electroreduction.

Metal-nitrogen-carbon single-atom catalysts (SACs) have recently emerged as selective electrocatalysts for the reduction of CO2 to CO, but their ability to further electroreduce CO is poor. Here, based on constant-potential density functional theory simulations, we predict that Co-N-M (M = Fe, Co) SACs with nonbonding metallic centers bridged by a common nitrogen atom can catalyze four-electron reduction of CO to methanol at an ultralow overpotential of 220-310 mV. We show that the metal atoms in the SACs are terminated by H species which prevent the formation of σ bonding between CO and the metal atoms. Thanks to the nonbonding electrostatic repulsion between Co and its adjacent M atom, the Co dxz band is broadened and shifted toward the Fermi level, leading to enhanced dxz - 2π* interaction that gives rise to stable CO adsorption and promotes its active and selective reduction. This work offers an alternative strategy to tackle the challenge of CO electroreduction on SACs and highlights the role of nonbonding metal-metal interactions in modulating adsorption properties of SACs.

Observation of Fast Low-Temperature Oxygen Ion Conduction in CeO2/ß"-Al2O3 Heterostructure.

Semiconductor ion fuel cells (SIFCs) have demonstrated impressive ionic conductivity and efficient power generation at temperatures below 600 °C. However, the lack of understanding of the ionic conduction mechanisms associated with composite electrolytes has impeded the advancement of SIFCs toward lower operating temperatures. In this study, a CeO2/ß″-Al2O3 heterostructure electrolyte is introduced, incorporating ß″-Al2O3 and leveraging the local electric field (LEF) as well as the manipulation of the melting point temperature of carbonate/hydroxide (C/H) by Na+ and Mg2+ from ß″-Al2O3. This design successfully maintains swift interfacial conduction of oxygen ions at 350 °C. Consequently, the fuel cell device achieved an exceptional ionic conductivity of 0.019 S/cm and a power output of 85.9 mW/cm2 at 350 °C. The system attained a peak power density of 1 W/cm2 with an ultra-high ionic conductivity of 0.197 S/cm at 550 °C. The results indicate that through engineering the LEF and incorporating the lower melting point C/H, there approach effectively observed oxygen ion transport at low temperatures (350 °C), effectively overcoming the issue of cell failure at temperatures below 419 °C. This study presents a promising methodology for further developing high-performance semiconductor ion fuel cells in the low temperature range of 300-600 °C.

Metabolomics analysis of the yolk of Zhijin white goose during the embryogenesis based on LC-MS/MS.

The egg yolk of the goose is rich in lipids, proteins and minerals, which is the main source of nutrition during the goose embryogenesis. Actually, the magnitude and variety of nutrients in yolk are dynamically changed to satisfy the nutritional requirements of different growth and development periods. The yolk sac membrane (YSM) plays a role in metabolizing and absorbing nutrients from the yolk, which are then consumed by the embryo or extra-fetal tissues. Therefore, identification of metabolites in egg yolk can help to reveal nutrient requirement in goose embryo. In this research, to explore the metabolite changes in egg yolk at embryonic day (E) 7, E12, E18, E23, and E28, we performed the assay using ultra-high performance liquid chromatography/tandem mass spectrometry (UHPLC-MS/MS). The findings showed that E7 and E12, E23 and E28 were grouped together, while E18 was significantly separated from other groups, indicating the changes of egg yolk development and metabolism. In total, 1472 metabolites were identified in the egg yolk of Zhijin white goose, and 636 differential metabolites (DMs) were screened, among which 264 were upregulated and 372 were downregulated. The Kyoto Encyclopedia of Genes and Genomes (KEGG) pathway analysis showed that the DMs were enriched in the biosynthesis and metabolism of amino acids, digestion and absorption of protein, citrate cycle (TCA cycle), aminoacyl-tRNA biosynthesis, phosphotransferase system (PTS), mineral absorption, cholesterol metabolism and pyrimidine metabolism. Our study may provide new ideas for improving prehatch embryonic health and nutrition.

Breaking the Scaling Relationship on Single-Atom Embedded MBene for Selective CO2 Electroreduction.

Highly active and selective electrochemical CO2 reduction reaction (CO2RR) to chemicals and fuels is crucial for clean energy production and environmental remediation. Although transition metals and their alloys are widely used to catalyze CO2RR, their activity and selectivity are generally unsatisfactory, hindered by energy scaling relationships among the reaction intermediates. Herein, we generalize the multisite functionalization strategy to single-atom catalysts in order to circumvent the scaling relationships for CO2RR. We predict that single transition metal atoms embedded in two-dimensional Mo2B2 could be exceptional catalysts for CO2RR. We show that the single-atoms (SAs) and their adjacent Mo atoms can only bind to carbon and oxygen atom, respectively, thus enabling dual site functionalization to circumvent the scaling relationships. Following extensive first-principles calculations, we discover two SA-Mo2B2 single-atom catalysts (SA = Rh and Ir) that can produce methane and methanol with an ultralow overpotential of -0.32 and -0.27 V, respectively.

Circumventing the scaling relationship on bimetallic monolayer electrocatalysts for selective CO2 reduction.

Electrochemical conversion of CO2 into value-added chemicals continues to draw interest in renewable energy applications. Although many metal catalysts are active in the CO2 reduction reaction (CO2RR), their reactivity and selectivity are nonetheless hindered by the competing hydrogen evolution reaction (HER). The competition of the HER and CO2RR stems from the energy scaling relationship between their reaction intermediates. Herein, we predict that bimetallic monolayer electrocatalysts (BMEs) - a monolayer of transition metals on top of extended metal substrates - could produce dual-functional active sites that circumvent the scaling relationship between the adsorption energies of HER and CO2RR intermediates. The antibonding interaction between the adsorbed H and the metal substrate is revealed to be responsible for circumventing the scaling relationship. Based on extensive density functional theory (DFT) calculations, we identify 11 BMEs which are highly active and selective toward the formation of formic acid with a much suppressed HER. The H-substrate antibonding interaction also leads to superior CO2RR performance on monolayer-coated penta-twinned nanowires.

Anti-dissolution Pt single site with Pt(OH)(O3)/Co(P) coordination for efficient alkaline water splitting electrolyzer.

As the most well-known electrocatalyst for cathodic hydrogen evolution in water splitting electrolyzers, platinum is unfortunately inefficient for anodic oxygen evolution due to its over-binding with oxygen species and excessive dissolution in oxidative environment. Herein we show that single Pt atoms dispersed in cobalt hydrogen phosphate with an unique Pt(OH)(O3)/Co(P) coordination can achieve remarkable catalytic activity and stability for oxygen evolution. The catalyst yields a high turnover frequency (35.1 ± 5.2 s-1) and mass activity (69.5 ± 10.3 A mg-1) at an overpotential of 300 mV and excellent stability. Mechanistic studies elucidate that the superior catalytic performance of isolated Pt atoms herein stems from optimal binding energies of oxygen intermediate and also their strong electronic coupling with neighboring Co atoms that suppresses the formation of soluble Ptx>4 species. Alkaline water electrolyzers assembled with an ultralow Pt loading realizes an industrial-level current density of 1 A cm-2 at 1.8 volts with a high durability.