Enhanced ferromagnetic properties achieved by F-doping in BaFe1-xMnxO3-δ.

Tailoring the crystal structure, spin, and charge state of perovskite oxides through fluorine ion doping is an attractive and effective strategy, which could significantly modify the physical and chemical properties of base oxides. Here, BaFe1-xMnxO3-δ (x = 0, 0.1, 0.2, 0.3) and BaFe1-xMnxO2.9-δF0.1 (x = 0.1, 0.2, 0.3), belonging to 6H-type BaFeO3-δ, are prepared and investigated to evaluate the impact of F- doping. The distortion of crystal structure and the reduced average valence of Mn and Fe confirm the preference for F- substitution in the hexagonal layer, which are found as the key factors for the improved magnetic properties, including ferromagnetic ordering temperature, coercive force, and remanent magnetization. Moreover, the valence reduction of B-site ions and the increased resistance distinctly indicate the expense of electron hole via fluorine doping. This work describes the adjustment of crystal structure, electronic configuration, and ferromagnetic performance by simple F- doping, which provides a prospect for practical magnetic materials.

Activating the Basal Planes and Oxidized Oxygens in Layer-Structured Na0.6 CoO2 for Boosted OER Activity.

With the CoO2 slabs consisting of Co4 O4 cubane structure, layered Nax CoO2 are considered promising candidates for oxygen evolution reaction (OER) in alkaline media given their earth-abundant and structural advantages. However, due to the strong adsorption of intermediates on the large basal planes, Nax CoO2 cannot meet the activity demands. Here, a novel one-pot synthesis strategy is proposed to realize the high solubility of iron in Nax CoO2 in an air atmosphere. The optimist Na0.6 Co0.9 Fe0.1 O2 exhibits enhanced OER activity compared to their pristine and other reported Fe-doped Nax CoO2 counterparts. Such an enhancement is mainly ascribed to the abundant active sites on the activated basal planes and the participation of oxidized oxygen as active sites independently, which breaks the scaling relationship limit in the OER process. This work is expected to contribute to the understanding of the modification mechanism of Fe-doped cobalt-based oxides and the exploitation of layer-structured oxides for energy application.

Rhodium and Carbon Sites with Strong d-p Orbital Interaction for Efficient Bifunctional Catalysis.

Efficient and stable catalysts are highly desired for the electrochemical conversion of hydrogen, oxygen, and water molecules, processes which are crucial for renewable energy conversion and storage technologies. Herein, we report the development of hollow nitrogenated carbon sphere (HNC) dispersed rhodium (Rh) single atoms (Rh1HNC) as an efficient catalyst for bifunctional catalysis. The Rh1HNC was achieved by anchoring Rh single atoms in the HNC matrix with an Rh-N3C1 configuration, via a combination of in situ polymerization and carbonization approach. Benefiting from the strong metal atom-support interaction (SMASI), the Rh and C atoms can collaborate to achieve robust electrochemical performance toward both the hydrogen evolution and oxygen reduction reactions in acidic media. This work not only provides an active site with favorable SMASI for bifunctional catalysis but also brings a strategy for the design and synthesis of efficient and stable bifunctional catalysts for diverse applications.

Highly Oxidized Oxide Surface toward Optimum Oxygen Evolution Reaction by Termination Engineering.

The oxygen evolution reaction (OER) is a critical step for sustainable fuel production through electrochemistry process. Maximizing active sites of nanocatalyst with enhanced intrinsic activity, especially the activation of lattice oxygen, is gradually recognized as the primary incentive. Since the surface reconfiguration to oxyhydroxide is unavoidable for oxygen-activated transition metal oxides, developing a surface termination like oxyhydroxide in oxides is highly desirable. In this work, we demonstrate an unusual surface termination of (111)-facet Co3O4 nanosheet that is exclusively containing edge-sharing octahedral Co3+ similar to CoOOH that can perform at approximately 40 times higher current density at 1.63 V (vs RHE) than commercial RuO2. It is found that this surface termination has an oxidized oxygen state in contrast to standard Co-O systems, which can serve as active site independently, breaking the scaling relationship limit. This work forwards the applications of oxide electrocatalysts in the energy conversion field by surface termination engineering.

Merging Platinum Single Atoms to Achieve Ultrahigh Mass Activity and Low Hydrogen Production Cost.

Single atom catalysts (SACs) with isolated active sites exhibit the highest reported mass activity for hydrogen evolution catalysis, which is crucial for practical applications. Here, we demonstrate that ultrahigh mass activity can also be achieved by rationally merging the isolated platinum (Pt) active sites in SAC. The catalyst was obtained by the thermodynamically driven diffusing and merging phosphorus-doped carbon (PC) supported Pt single atoms (Pt1@PC) into Pt nanoclusters (PtM@PC). X-ray absorption spectroscopy analysis revealed that the merged nanoclusters exhibit much stronger interactions with the support than the traditional method, enabling more efficient electron transfer. The optimized PtM@PC exhibited an order of magnitude higher mass activity (12.7 A mgPt-1) than Pt1@PC (0.9 A mgPt-1) at an overpotential of 10 mV in acidic media, which is the highest record to date, far exceeding reports for other outstanding SACs. Theoretical study revealed that the collective active sites in PtM@PC exhibit both favorable hydrogen binding energy and fast reaction kinetics, leading to the significantly enhanced mass activity. Despite its low Pt content (2.2 wt %), a low hydrogen production cost of ∼3 USD kg-1 was finally achieved in the full-water splitting at a laboratory scale.

Synthesis of stable γ-phase MnS1-xSex nanoflakes with inversion symmetry breaking.

Inversion symmetry breaking plays a critical role in the formation of magnetic skyrmions. Therefore, for the application of skyrmion-based devices, it is important to develop novel engineering techniques and explore new non-centrosymmetric lattices. In this paper, we report the rational synthesis of stable γ-phase MnS1-xSex (0 ≤ x ≤ 0.45) nanoflakes with an asymmetric distribution of the elemental content, which persists on inversion symmetry breaking. The temperature dependence of resonant second-harmonic generation characterization reveals that a non-centrosymmetric crystal structure exists in our as-grown γ-phase MnS1-xSex with spatial-inversion symmetry breaking. By tuning the parameters of nucleation temperature and growth time, we produced a detailed growth phase diagram, revealing a controllable as-grown structure evolution from γ-phase wurtzite-type to α-phase rock-salt type structure of MnS1-xSex nanoflakes. Our work provides a new playground to explore novel materials that have broken inversion symmetry.

Tin Nanoclusters Confined in Nitrogenated Carbon for the Oxygen Reduction Reaction.

The oxygen reduction reaction is essential for fuel cells and metal-air batteries in renewable energy technologies. Developing platinum-group-metal (PGM)-free catalysts with comparable catalytic performance is highly desired for cost efficiency. Here, we report a tin (Sn) nanocluster confined catalyst for the electrochemical oxygen reduction. The catalyst was fabricated by confining 1-1.5 nm sized Sn nanoclusters in situ in microporous nitrogen-doped carbon polyhedra (SnxNC) with an average pore size of 0.7 nm. SnxNC exhibited high catalytic performance in acidic media, including positive onset and half-wave potentials, comparable to those of the state-of-the-art Pt/C and far exceeding those of the Sn single-atom catalyst. Combined structural and theoretical analyses reveal that the confined Sn nanoclusters, which have favorable oxygen adsorption behaviors, are responsible for the high catalytic performance, but not Sn single atoms.

Regulating Na Occupation to Introduce Non-Fermi-Liquid States of NaxCoO2 for Enhanced Water Oxidation Activity.

The couplings among fundamental quantum parameters provide versatile freedom of manipulations for useful electronic structures, based on which optimized oxygen evolution reaction (OER) performances can be achieved. In this work, we demonstrate the successful regulation of the electronic structure in layered NaxCoO2 oxides to introduce a non-Fermi-liquid (NFL) state by adjusting the Na content and Na occupation in the lattice. The presence of an NFL is facilitated by the weakened electron-electron correlation when the on-site Coulomb repulsion of Co4+ with Na+ and oxygen vacancy with Na+ is balanced. As a feature of NFL, the metallic states in the vicinity of the Fermi energy contribute to a fast electron transfer efficiency and eventually to an improved OER performance. These findings open up a new avenue to design highly efficient OER electrocatalysts in strong electron-correlated transition metal material systems by consideration of couplings among the fundamental quantum parameters.

Zn-doped NiSe2@Ni(OH)2 nanocomposites as binder-free electrodes for asymmetric supercapacitors with impressive performance.

The low stability and poor activities of transition metal selenides (TMSs) in alkaline electrolyte limit their application in supercapacitors. Metal doping and hybridization of various electroactive materials with different properties are utilized to enhance the electrochemical performance of TMSs by optimizing their electronic structure and providing rich electrochemical active sites. Herein, we report a simple two-step hydrothermal method for the growth of Zn-doped NiSe2 and Ni(OH)2 nanocomposites on Ni foam [Zn-NiSe2/Ni(OH)2]. The resulting material delivers high specific capacity (1525.8 C g-1/564.7 mA h g-1 at 6 A g-1 and 1220 C g-1 at 10 A g-1) in a three-electrode system. A Zn-NiSe2/Ni(OH)2//porous carbon (PC) aqueous asymmetric supercapacitor (ASC) was built by utilizing Zn-NiSe2/Ni(OH)2 as the positive electrode and PC as the negative electrode. This Zn-NiSe2/Ni(OH)2//PC ASC shows an energy density of 75.8 W h kg-1 at a power density of 916.1 W kg-1 and achieves a specific capacity retention of 100% after 25 000 cycles at 10 A g-1. These results reveal that the Zn doping and the hybridization of NiSe2 with Ni(OH)2 can obtain impressive electrochemical properties in ASCs.

Surface Electronic Modulation with Hetero-Single Atoms to Enhance Oxygen Evolution Catalysis.

Oxygen evolution catalysis plays a crucial role in the solar-to-fuel conversion for green energy applications. However, developing efficient and stable catalysts for the oxygen evolution catalysis remains a great challenge. Here, we successfully activate an inefficient oxygen evolution catalyst using a simple single atom tailoring strategy. The Rh element with its unfilled 4d8 electron configuration was selected to atomically implant into a Cu oxide matrix, which has a filled 3d10 electron configuration. The hetero-Rh single atom (SA) migration was achieved by dispersing Cu2O nanocubes in a RhCl3 aqueous solution, enabling an ion exchange process. The activated catalyst (Cu2O-RhSA) exhibited significantly enhanced catalytic activity toward oxygen evolution in alkaline media, surpassing the performance of pristine Cu2O nanocubes and commercial IrO2. A theoretical study further confirmed that the migrated hetero-Rh SAs can tailor the interaction between the Cu and O sites, modulating the electron density distribution on the surface of Cu2O, leading to a more favorable oxygen evolution process.

Properties of diamane anchored with different groups.

The two-dimensional counterpart of diamond, diamane, has attracted increasing interest due to its potentially distinctive properties. In this paper, diamanes anchored with different anion groups have been systematically studied with density functional theory (DFT) for the first time. Among them 12 conformers are confirmed to be stable and present direct semiconductor features with bandgaps ranging from 2.527 eV to 4.153 eV, and the in-plane stiffness is larger than that of graphene. Moreover, the electron carrier mobility of chair2-F is exceptionally high at 16546.713 cm2 V-1 s-1 along the y-direction, which is remarkably larger than that of diamond; and N-, B-doped boat2-H can be doped to have n-, p-type conductivity with a moderate activation energy of 0.34 and 0.37 eV, respectively. This work suggests that functionalized diamanes are promising for electronic devices and engineering materials.

Stable and efficient solar-driven photoelectrochemical water splitting into H2 and O2 based on a BaTaO2N photoanode decorated with CoO microflowers.

Stable and efficient photoelectrochemical water splitting has been achieved using a BaTaO2N photoanode decorated with CoO microflowers. The CoO microflowers effectively collect holes from BaTaO2N which kinetically protects BaTaO2N against photocorrosion. A Faraday efficiency of almost unity (99.2%) has been recorded for O2 evolution reactions. The tips of the CoO microflowers are the most active sites for water oxidation reactions.

Emerging flat bands in large-angle twisted bi-layer graphene under pressure.

Recent experiments on magic-angle twisted bi-layer graphene have attracted intensive attention due to exotic properties such as unconventional superconductivity and correlated insulation. These phenomena were often found at a magic angle less than 1.1°. However, the preparation of precisely controlled bi-layer graphene with a small magic angle is challenging. In this work, electronic properties of large-angle twisted bi-layer graphene (TBG) under pressure are investigated with density functional theory. We demonstrate that large-angle TBG can display flat bands nearby the Fermi level under pressure, which may also induce interesting properties such as superconductivity which have only been found in small-angle TBG at ambient pressure. The Fermi velocity is found to decrease monotonously with pressure for large twisted angles, e.g., 21.8°. Our work indicates that applying pressure provides opportunities for flat-band engineering in larger angle TBG and supports further exploration in related investigations.

Hydrogen Generation and Degradation of Organic Dyes by New Piezocatalytic 0.7BiFeO3-0.3BaTiO3 Nanoparticles with Proper Band Alignment.

Piezoelectric materials have recently demonstrated their potential applications in clean energy exploration and environmental remediation through triggering a number of catalytic reactions by harvesting waste vibrational energy in the environment. In this work, unique lead-free 0.7BiFeO3-0.3BaTiO3 (BF-BT) nanoparticles with tuned band structure were synthesized by the hydrothermal method for use as piezoelectric catalysts to generate hydrogen by splitting water; a high production rate of 1.322 mmol/g was achieved in 1 h, which is 10 times higher than the production rate of pure BiFeO3. Of particular interest, BF-BT particles attached to nickel mesh have the ability to degrade rhodamine B in flowing water, demonstrating their potential to treat polluted water by anchoring BF-BT in drains. Finally, we propose novel insight on the piezocatalytic mechanism, which is based on the internal electric field (the sum of the depolarization field and the screening charge field) that drives electron/hole separation and movement.

Mechanochemistry for ammonia synthesis under mild conditions.

Ammonia, one of the most important synthetic feedstocks, is mainly produced by the Haber-Bosch process at 400-500 °C and above 100 bar. The process cannot be performed under ambient conditions for kinetic reasons. Here, we demonstrate that ammonia can be synthesized at 45 °C and 1 bar via a mechanochemical method using an iron-based catalyst. With this process the ammonia final concentration reached 82.5 vol%, which is higher than state-of-the-art ammonia synthesis under high temperature and pressure (25 vol%, 450 °C, 200 bar). The mechanochemically induced high defect density and violent impact on the iron catalyst were responsible for the mild synthesis conditions.

High Oxygen Evolution Activity of Tungsten Bronze Oxides Boosted by Anchoring of Co2+ at Nb5+ Sites Accompanied by Substantial Oxygen Vacancy.

The participation of lattice oxygen in the oxygen evolution reaction (OER) process has been proved to be faster in kinetics than the mechanisms where only metal is involved, although activating the lattice oxygen in the traditional rigid structures remains a big challenge. In this work, efforts are devoted to exploring a new flexible structure that is competent in providing large amounts of oxygen vacancies as well as offering the freedom to manipulate the electronic structure of metal cations. This is demonstrated by anchoring low valence state Co at high valence state Nb sites in the tetragonal tungsten bronze (TTB)-structured Sr0.5Ba0.5Nb2- x Co x O6-δ , with different ratios of Co to Nb to optimize the Co substitution proportion. It is found that the occupation of Co in the Nb5+ sites gives rise to the generation of massive surface oxygen vacancies (Ovac), while Co itself is stabilized in Co2+ by adjacent Ovac. The coexistence of Ovac and LS Co2+ enables an oxygen intercalation mechanism in the optimal SBNC45 with specific activity at 1.7 V versus reversible hydrogen electrode that is 20 times higher than for the commercial IrO2. This work illuminates an entirely new avenue to rationally design OER electrocatalysts with ultrafast kinetics.

Interfacial Titanium Diffusion Self-Adapting Layer in Ultrathin Epitaxial MnO2/TiO2 Heterostructures.

The electrochemical performance of supercapacitors is suppressed by a large number of defects in the interface of heterostructure due to lattice mismatch. In this paper, the (001) oriented rutile MnO2 thin films with different thicknesses were grown on rutile TiO2 substrates. The lattice mismatch between film and substrate was minimized through a Ti diffusion self-adapting layer. The energy-dispersive spectroscopy mappings were used to measure the diffusion range of Ti. The results of high-resolution X-ray diffraction confirmed that the dependence of the out-of-plane lattice parameter on the thickness was consistent with the self-adapting interface model, indicating that Ti diffusion can indeed alleviate the lattice mismatch. In addition, the results of the synchrotron soft X-ray absorption spectrum indicated that the capacitance of the thin films with a large proportion of Ti diffusion increased with electrons involved in the reaction. Although the decrease of carrier density and conductivity of the thinner films depressed the electrochemical activity, it is worth mentioning that the film we designed still has considerable specific capacitance even when it is very thin, which can provide a new idea for the development of thinner and larger capacity potential micro-supercapacitors.

Revealing Isolated M-N3 C1 Active Sites for Efficient Collaborative Oxygen Reduction Catalysis.

Single atom catalysts (SACs) are of great importance for oxygen reduction, a critical process in renewable energy technologies. The catalytic performance of SACs largely depends on the structure of their active sites, but explorations of highly active structures for SAC active sites are still limited. Herein, we demonstrate a combined experimental and theoretical study of oxygen reduction catalysis on SACs, which incorporate M-N3 C1 site structure, composed of atomically dispersed transition metals (e.g., Fe, Co, and Cu) in nitrogenated carbon nanosheets. The resulting SACs with M-N3 C1 sites exhibited prominent oxygen reduction catalytic activities in both acidic and alkaline media, following the trend Fe-N3 C1 > Co-N3 C1 > Cu-N3 C1 . Theoretical calculations suggest the C atoms in these structures behave as collaborative adsorption sites to M atoms, thanks to interactions between the d/p orbitals of the M/C atoms in the M-N3 C1 sites, enabling dual site oxygen reduction.

Analysis of Flavonoid Compounds by Terahertz Spectroscopy Combined with Chemometrics.

Flavonoids are a large class of polyphenols widely distributed in plants in the free form or as glycosides, and they have antioxidation, antibacterial, antitumor growth, and other pharmacological effects. As an important active component of traditional Chinese medicine, they have high medicinal value and development prospects. In this work, the biomolecular properties of 10 common flavonoids, including baicalein, baicalin, apigenin, quercetin, naringenin, hesperetin, daidzein, genistein, puerarin, and gastrodin, are studied by terahertz time-domain spectroscopy (THz-TDS) in the range of 0.2-2.5 THz. The results reveal that these flavonoids have different characteristic absorption peaks in the terahertz band. Moreover, the terahertz absorption characteristics of samples in the temperature range of 78-320 K are studied. The results show that the characteristic absorption peaks gradually increase with the decrease in temperature, and the frequency position of the absorption peak has a slight blue shift. Furthermore, qualitative identification and quantitative analysis of flavonoids are carried out by terahertz spectra combined with chemometrics. Specifically, a series of mixtures of three flavonoids with similar molecular structures under various concentrations are analyzed. The partial least-squares regression (PLSR) model and the artificial neural network (ANN) model are applied to quantitatively analyze the ternary mixture. The results confirm that the ANN model obtains the best predicted value, with the root-mean-square errors in the prediction set (RMSEP) of 1.27% for daidzein. In summary, the biomolecular properties of flavonoids are studied by the THz-TDS technique, and a rapid, effective, and nondestructive method for qualitative identification and quantitative analysis of flavonoids is provided. The results demonstrate that this method has potential application value in the detection of Chinese herbal medicine and has better referential significance for the study of other biomolecules, especially for isomers or similar molecular structures.

Building and identifying highly active oxygenated groups in carbon materials for oxygen reduction to H2O2.

The one-step electrochemical synthesis of H2O2 is an on-site method that reduces dependence on the energy-intensive anthraquinone process. Oxidized carbon materials have proven to be promising catalysts due to their low cost and facile synthetic procedures. However, the nature of the active sites is still controversial, and direct experimental evidence is presently lacking. Here, we activate a carbon material with dangling edge sites and then decorate them with targeted functional groups. We show that quinone-enriched samples exhibit high selectivity and activity with a H2O2 yield ratio of up to 97.8 % at 0.75 V vs. RHE. Using density functional theory calculations, we identify the activity trends of different possible quinone functional groups in the edge and basal plane of the carbon nanostructure and determine the most active motif. Our findings provide guidelines for designing carbon-based catalysts, which have simultaneous high selectivity and activity for H2O2 synthesis.