Combination of nanoparticles with single-metal sites synergistically boosts co-catalyzed formic acid dehydrogenation.

The development of hydrogen technologies is at the heart of a green economy. As prerequisite for implementation of hydrogen storage, active and stable catalysts for (de)hydrogenation reactions are needed. So far, the use of precious metals associated with expensive costs dominates in this area. Herein, we present a new class of lower-cost Co-based catalysts (Co-SAs/NPs@NC) in which highly distributed single-metal sites are synergistically combined with small defined nanoparticles allowing efficient formic acid dehydrogenation. The optimal material with atomically dispersed CoN2C2 units and encapsulated 7-8 nm nanoparticles achieves an excellent gas yield of 1403.8 mL·g-1·h-1 using propylene carbonate as solvent, with no activity loss after 5 cycles, which is 15 times higher than that of the commercial Pd/C. In situ analytic experiments show that Co-SAs/NPs@NC enhances the adsorption and activation of the key intermediate monodentate HCOO*, thereby facilitating the following C-H bond breaking, compared to related single metal atom and nanoparticle catalysts. Theoretical calculations show that the integration of cobalt nanoparticles elevates the d-band center of the Co single atoms as the active center, which consequently enhances the coupling of the carbonyl O of the HCOO* intermediate to the Co centers, thereby lowering the energy barrier.

Plasma-assisted manipulation of vanadia nanoclusters for efficient selective catalytic reduction of NOx.

Supported nanoclusters (SNCs) with distinct geometric and electronic structures have garnered significant attention in the field of heterogeneous catalysis. However, their directed synthesis remains a challenge due to limited efficient approaches. This study presents a plasma-assisted treatment strategy to achieve supported metal oxide nanoclusters from a rapid transformation of monomeric dispersed metal oxides. As a case study, oligomeric vanadia-dominated surface sites were derived from the classic supported V2O5-WO3/TiO2 (VWT) catalyst and showed nearly an order of magnitude increase in turnover frequency (TOF) value via an H2-plasma treatment for selective catalytic reduction of NO with NH3. Such oligomeric surface VOx sites were not only successfully observed and firstly distinguished from WOx and TiO2 by advanced electron microscopy, but also facilitated the generation of surface amide and nitrates intermediates that enable barrier-less steps in the SCR reaction as observed by modulation excitation spectroscopy technologies and predicted DFT calculations.

A Multistate Non-Volatile Photoelectronic Memory Device Based on Ferroelectric Tunnel Junction with Modulable Visible Light Photoresponse.

Recently, certain ferroelectric tunnel junctions (FTJs) exhibit non-volatile modulations on photoresponse as well as tunneling electroresistance (TER) effects related to ferroelectric polarization states. From the opposite perspective, the corresponding polarization states can be read by detecting the levels of the photocurrent. In this study, we fabricate a novel amorphous selenium (a-Se)/PbZr0.2Ti0.8O3 (PZT)/Nb-doped SrTiO3 (NSTO) heterojunction, which exhibits a high TER of 3 × 106. Unlike perovskite oxide FTJs with a limited ultraviolet response, the introduction of a narrow bandgap semiconductor (a-Se) enables self-powered photoresponse within the visible light range. The self-powered photoresponse characteristics can be significantly modulated by ferroelectric polarization. The photocurrent after writing polarization voltages of +4 and -5 V exhibits a 1200% increase. Furthermore, the photocurrent could be clearly distinguished after writing stepwise polarization voltages, and then a multistate information storage is designed with nondestructive readout capacity under light illumination. This work holds great significance in advancing the development of ferroelectric multistate photoelectronic memories with high storage density and expanding the design possibilities for FTJs.

Complex Materials with Stochastic Structural Patterns: Spiky Colloids with Enhanced Charge Storage Capacity.

Self-assembled materials with complex nanoscale and mesoscale architecture attract considerable attention in energy and sustainability technologies. Their high performance can be attributed to high surface area, quantum effects, and hierarchical organization. Delineation of these contributions is, however, difficult because complex materials display stochastic structural patterns combining both order and disorder, which is difficult to be consistently reproduced yet being important for materials' functionality. Their compositional variability make systematic studies even harder. Here, a model system of FeSe2 "hedgehog" particles (HPs) was selected  to gain insight into the mechanisms of charge storage n complex nanostructured materials common for batteries and supercapacitors. Specifically, HPs represent self-assembled biomimetic nanomaterials with a medium level of complexity; they display an organizational pattern of spiky colloids with considerable disorder yet non-random; this patternt is consistently reproduced from particle to particle. . It was found that HPs can accommodate ≈70× greater charge density than spheroidal nano- and microparticles. Besides expanded surface area, the enhanced charge storage capacity was enabled by improved hole transport and reversible atomic conformations of FeSe2 layers in the blade-like spikes associated with the rotatory motion of the Se atoms around Fe center. The dispersibility of HPs also enables their easy integration into energy storage devices. HPs quadruple stored electrochemical energy and double the storage modulus of structural supercapacitors.

Atomically Dispersed Cobalt/Copper Dual-Metal Catalysts for Synergistically Boosting Hydrogen Generation from Formic Acid.

The development of practical materials for (de)hydrogenation reactions is a prerequisite for the launch of a sustainable hydrogen economy. Herein, we present the design and construction of an atomically dispersed dual-metal site Co/Cu-N-C catalyst allowing significantly improved dehydrogenation of formic acid, which is available from carbon dioxide and green hydrogen. The active catalyst centers consist of specific CoCuN6 moieties with double-N-bridged adjacent metal-N4 clusters decorated on a nitrogen-doped carbon support. At optimal conditions the dehydrogenation performance of the nanostructured material (mass activity 77.7 L ⋅ gmetal -1 ⋅ h-1 ) is up to 40 times higher compared to commercial 5 % Pd/C. In situ spectroscopic and kinetic isotope effect experiments indicate that Co/Cu-N-C promoted formic acid dehydrogenation follows the so-called formate pathway with the C-H dissociation of HCOO* as the rate-determining step. Theoretical calculations reveal that Cu in the CoCuN6 moiety synergistically contributes to the adsorption of intermediate HCOO* and raises the d-band center of Co to favor HCOO* activation and thereby lower the reaction energy barrier.

Giant electrically tunable magnon transport anisotropy in a van der Waals antiferromagnetic insulator.

Anisotropy is a manifestation of lowered symmetry in material systems that have profound fundamental and technological implications. For van der Waals magnets, the two-dimensional (2D) nature greatly enhances the effect of in-plane anisotropy. However, electrical manipulation of such anisotropy as well as demonstration of possible applications remains elusive. In particular, in-situ electrical modulation of anisotropy in spin transport, vital for spintronics applications, has yet to be achieved. Here, we realized giant electrically tunable anisotropy in the transport of second harmonic thermal magnons (SHM) in van der Waals anti-ferromagnetic insulator CrPS4 with the application of modest gate current. Theoretical modeling found that 2D anisotropic spin Seebeck effect is the key to the electrical tunability. Making use of such large and tunable anisotropy, we demonstrated multi-bit read-only memories (ROMs) where information is inscribed by the anisotropy of magnon transport in CrPS4. Our result unveils the potential of anisotropic van der Waals magnons for information storage and processing.

Improved Dual-Polarity Response via Pyro-phototronic Effect for Filterless Visible Light Communication.

Dual-polarity response photodetectors (PDs) take full advantage of the directivity of the photocurrent to identify optical information. The dual-polarity signal ratio, a key parameter that represents the equilibrium degree of responses to different lights, is proposed for the first time. The synchronous enhancement of dual-polarity photocurrents and the amelioration of the dual-polarity signal ratio are beneficial to the practical applications. Herein, based on the selective light absorption and energy band structure design, a self-powered CdS/PEDOT:PSS/Au heterojunction PD consisting of a p-n junction and a Schottky junction exhibits unique wavelength-dependent dual-polarity response, where the photocurrent is negative and positive in the short and long wavelength regions, respectively. More importantly, the pyro-phototronic effect inside the CdS layer significantly improves the dual-polarity photocurrents with the maximum enhancement factors of 120%, 343%, 1167%, 1577%, and 1896% at 405, 450, 532, 650, and 808 nm, respectively. Furthermore, the dual-polarity signal ratio tends to 1:1 due to different degrees of the enhancement. This work provides a novel design strategy for dual-polarity response PDs with a simple working principle and improved performance, which can supply a substitution for two traditional PDs in the filterless visible light communication (VLC) system.

Extraordinary deactivation offset effect of zinc and arsenic on V2O5 -WO3/TiO2 catalysts: Like cures like.

The commercial V2O5 -WO3/TiO2 (VWTi) catalysts often suffer from a serious joint deactivation by multiple heavy metals in the flue gas for NOx removal by NH3-SCR. Herein, we report an extraordinary deactivation offset effect between Zn and As on VWTi with alleviation of the toxic effects of the heavy metals by "like cures like". With the As&Zn content of 4 wt%, VWTi-As&Zn exhibited over 97% NO conversion under a GHSV of 100,000 h-1 and good SO2/H2O tolerance (> 93% NO conversion). It's presented 85% of fresh VWTi, exceeding those of VWTi-Zn (15%) by 5.6-fold and VWTi-As (70%) by 1.2-fold. Structure analysis showed that, unlike VWTi-As and VWTi-Zn, the VO vibration and dispersion state of VOx sites over VWTi-As&Zn were hardly affected. Moreover, VWTi-As&Zn possessed both the Lewis and Brønsted acid sites while VWTi-Zn and VWTi-As had only one type of them. The operando infrared/Raman/UV-vis spectroscopy and DFT calculations verified that the less affected VOx sites mainly reflected in three aspects: 1) the electron interaction between As and Zn; 2) the active VO Lewis acid sites; 3) lower energy barrier for N - H bond breaking. The "like cures like" phenomenon may open up an innovative pathway for the control of hazardous heavy metals.

Heterostrain-enabled ultrahigh electrostrain in lead-free piezoelectric.

Piezoelectric materials provide high strain and large driving forces in actuators and can transform electrical energy into mechanical energy. Although they were discovered over 100 years ago, scientists are still searching for alternative lead-free piezoelectrics to reduce their environmental impact. Developing high-strain piezoelectric materials has been a long-term challenge, particularly challenging for the design of high-strain polycrystalline piezoelectrics containing no toxic lead element. In this work, we report one strategy to enhance the electrostrain via designing "heterostrain" through atomic-scale defect engineering and mesoscale domain engineering. We achieve an ultrahigh electrostrain of 2.3% at high temperature (220 °C) in lead-free polycrystalline ceramics, higher than all state-of-the-art piezoelectric materials, including lead-free and lead-based ceramics and single crystals. We demonstrate practical solutions for achieving high electrostrain in low-cost environmentally piezoelectric for various applications.

A triatomic carbon and derived pentacarbides with superstrong mechanical properties.

Diamond has the largest hardness of any natural material with an experimental Vickers hardness value of 90-150 GPa. Here, we reported the stable triatomic carbon allotrope with giant hardness closing that of diamond and a family of pentacarbides with superstrong mechanical properties from the state-of-the-art theoretical calculations. The triatomic carbon allotrope can be transformed into a two-dimensional carbon monolayer at a high temperature. We predicted that the triatomic carbon allotrope holds a hardness of 113.3 GPa, showing the potential capability of cracking diamond. Substitution with Al, Fe, Ir, Os, B, N, Si, W, and O element resulted in strong pentacarbides with Young's modulus of 400-800 GPa. SiC5, BC5, IrC5, and WC5 are superhard materials with Vickers hardness over 40 GPa, of which BC5 was successfully synthesized in previous experimental reports. Our results demonstrated the potential of the present strong triatomic carbon and pentacarbides as future high-performance materials.

Optimal control of the compositions, interfaces, and defects of hollow sulfide for electromagnetic wave absorption.

The aimlessness in the selection of dielectric absorbing materials and the regulation of complex permittivity consumes time and resources. It is an effective way to construct electromagnetic wave (EMW)-absorbing materials dominated by dielectric loss to select materials and adjust complex permittivity based on theory. With sulfide as an example, a hollow ZnO/ZnS composite was constructed using ZnO as a hard template. Subsequently, based on the diverse binding ability of Cu and Zn ions to S ions, the compositions, interfaces, and defects of the sample were simultaneously regulated. There was competition and synergy between the relaxation process caused by the defects and interfaces and the conductivity loss, resulting in the regulation of complex permittivity. Furthermore, the hollow structure effectively reduced the density of the material and improved the impedance matching ability of the sample. As a result, the effective absorption bandwidth (EAB) of the hollow nanoflower ZnO/ZnS/CuS composite reached 5.2 GHz (from 12.8 to 18 GHz) with a matching thickness of 1.59 mm. This method provides a direction for ameliorating the complex permittivity of EMW-absorbing materials dominated by dielectric loss to realize broadband absorption.

Multiphase Engineered BNT-Based Ceramics with Simultaneous High Polarization and Superior Breakdown Strength for Energy Storage Applications.

Dielectric ceramics are crucial for high-temperature, pulse-power energy storage applications. However, the mutual restriction between the polarization and breakdown strength has been a significant challenge. Here, multiphase engineering controlled by the two-step sintering heating rate is adopted to simultaneously obtain a high polarization and breakdown strength in 0.8(0.95Bi0.5Na0.5TiO3-0.05SrZrO3)-0.2NaNbO3 (BNTSZNN) ceramic systems. The coexistence of tetragonal (T) and rhombohedral (R) phases benefits the temperature stability of BNTSZNN ceramics. Increasing the heating rate during sintering reduces the diffusion of SrZrO3 and NaNbO3 into Bi0.5Na0.5TiO3, which results in a high proportion of the R phase and a finer grain size. The overall polarization is enhanced by increasing the proportion of the high-polarization R phase, which is demonstrated using a first-principles method. Meanwhile, the finer grain size enhances the breakdown strength. Following this design philosophy, an ultrahigh Wdis of 5.55 J/cm3 and η above 85% is achieved in BNTSZNN ceramics as prepared with a fast heating rate of 60 °C/min given a simultaneously high polarization of 43 µC/cm2 and high breakdown strength of 350 kV/cm. Variations in the discharge energy density from room temperature to 160 °C are less than 10%. Additionally, such BNTSZNN ceramics exhibit an ultrafast discharge speed with τ0.9 at approximately 60 ns, which shows great potential in pulse-power system applications.

Interfacial Bonding and Electronic Structure between Copper Thiocyanate and Hybrid Organohalide Lead Perovskites for Photovoltaic Application.

Interface engineering of halide perovskite solar-cell device layers has been showing potential for the enhancement of efficiency and stability. The replacement of spiro-OMeTAD with cheap hole extraction layer CuSCN has emerged as one effective method for the long-term large-scale application. To clarify the interfacial mechanism between the halide perovskite layer and the CuSCN layer, first-principles calculations were performed. An interface-induced electrostatic potential increase and electron-hole excitation were observed at the interfaces. A Cu-I bond and a Pb-N bond were formed at the interface. The MAI interface exhibited a larger ionic displacement and a higher interface-induced potential than the PbI interface. Strong hybridization among Cu 4d, I 5p, N 2p, and Pb 6p orbitals at the interface was found to be the origin of the electron-hole excitation, interface reconstruction, electron charge redistribution, and stability enhancement.

Graphene-like monolayer monoxides and monochlorides.

Two-dimensional monolayer materials, with thicknesses of up to several atoms, can be obtained from almost every layer-structured material. It is believed that the catalogs of known 2D materials are almost complete, with fewer new graphene-like materials being discovered. Here, we report 2D graphene-like monolayers from monoxides such as BeO, MgO, CaO, SrO, BaO, and rock-salt structured monochlorides such as LiCl, and NaCl using first-principle calculations. Two-dimensional materials containing d-orbital atoms such as HfO, CdO, and AgCl are predicted. Adopting the same strategy, 2D graphene-like monolayers from mononitrides such as scandium nitride (ScN) and monoselenides such as cadmium selenide (CdSe) are discovered. Stress engineering is found to help stabilize 2D monolayers, through canceling the imaginary frequency of phonon dispersion relation. These 2D monolayers show high dynamic, thermal, kinetic, and mechanic stabilities due to atomic hybridization, and electronic delocalization.

Orientation-Dependent Optical Magnetoelectric Effect in Patterned BaTiO3/La0.67Sr0.33MnO3 Heterostructures.

The optical magnetoelectric effect has been widely investigated, but obtaining the large and tunable optical magnetoelectric effect at room temperature is still a big challenge. We here design ferroelectric/ferromagnetic heterostructures with various orientations, which are composed of titanate BaTiO3 and manganese oxide La0.67Sr0.33MnO3. This artificial bilayer structure presents room-temperature ferroelectric and ferromagnetic properties. After patterning a 4 µm grating structure on the bilayer thin film, the optical magnetoelectric effect for near-infrared light is investigated systematically through the Bragg diffraction method. The relative change of diffracted light intensity of the order n = 1 has a strong dependence on the magnetization and polarization of the thin films, whether the superlattice is irradiated in reflection or transmission geometries. For (100)- and (111)-oriented samples, both show the room-temperature optical magnetoelectric effect, while the (111)-oriented thin film has a stronger optical magnetoelectric effect. These results pave the way for designing next-generation optical magnetoelectric devices based on the ferroelectric/ferromagnetic structure.

The Frustration-induced Ferroelectricity of a Manganite Tricolor Superlattice with Artificially Broken Symmetry.

In this paper, [(La0.9Sr0.1MnO3)n/(Pa0.9Ca0.1MnO3)n/(La0.9Sb0.1MnO3)n]m superlattices films have been deposited on (001) Nb:SrTiO3 substrates by a laser molecular-beam epitaxy technology. Expected ferroelectricity arise at well-defined tricolor superlattice at low temperature, composed of transition metal manganite, which is absent in the single-phase compounds. Furthermore, the ferroelectric properties of the superlattices are enhanced by increasing the periodicity m, which may be attributed to the accumulation of the polarization induced by the frustration. As for the magnetic hysteresis loop characteristics of the multilayer structures, the saturation magnetization and magnetic coercivity of films present definitely a strong periodic dependence. It also indicates that the frustration may exist in the tricolor superlattice. Our results further verify the previous theoretical research of generating multiferroics experimentally paving a way for designing or developing the novel magnetoelectric devices based on manganite ferromagnets.

Enhanced Energy-Storage Density and High Efficiency of Lead-Free CaTiO3-BiScO3 Linear Dielectric Ceramics.

A novel lead-free (1 - x)CaTiO3-xBiScO3 linear dielectric ceramic with enhanced energy-storage density was fabricated. With the composition of BiScO3 increasing, the dielectric constant of (1 - x)CaTiO3-xBiScO3 ceramics first increased and then decreased after the composition x > 0.1, while the dielectric loss decreased first and increased. For the composition x = 0.1, the polarization was increased into 12.36 µC/cm2, 4.6 times higher than that of the pure CaTiO3. The energy density of 0.9CaTiO3-0.1BiScO3 ceramic was 1.55 J/cm3 with the energy-storage efficiency of 90.4% at the breakdown strength of 270 kV/cm, and the power density was 1.79 MW/cm3. Comparison with other lead-free dielectric ceramics confirmed the superior potential of CaTiO3-BiScO3 ceramics for the design of ceramics capacitors for energy-storage applications. First-principles calculations revealed that Sc subsitution of Ti-site induced the atomic displacement of Ti ions in the whole crystal lattice, and lattice expansion was caused by variation of the bond angles and lenghths. Strong hybridization between O 2p and Ti 3d was observed in both valence band and conduction band; the hybridization between O 2p and Sc 3d at high conduction band was found to enlarge the band gap, and the static dielectric tensors were increased, which was the essential for the enhancement of polarization and dielectric properties.

Thermal mismatch strain induced disorder of Y2Mo3O12 and its effect on thermal expansion of Y2Mo3O12/Al composites.

Fully dense Y2Mo3O12/Al composites were prepared by squeeze-casting. Relatively mild conditions of 750 °C/20 min/50 MPa were used in order to avoid reaction of the components. SEM, Raman spectroscopy, XRD and dilatometry were used to characterize the microstructures and morphologies of the composites. Zero thermal expansion was achieved in the temperature range where the thermal mismatch strain was zero. We show that the CTE mismatch of Al and Y2Mo3O12 results in compressive and tensile strains that distort the Y2Mo3O12 lattice. We establish a novel method to measure the negative thermal expansion (NTE) materials' CTE under strain by measuring the composites' CTE and calculating the thermal mismatch strain between the NTE ceramic and the metal matrix. The relationship between thermal strain and Raman shift is established and measured and the simulated results are in good agreement. We also find Y2Mo3O12 to have a positive CTE when the surface strain is ≥0.80 × 10-2%.

Polarization Switching and Photoinduced Dielectric and Ferroelectric Properties in YMnO3/La0.67Sr0.33MnO3 Heterostructure.

YMnO3/La0.67Sr0.33MnO3 heterostructure was fabricated on SrTiO3 (110) substrate by pulse laser deposition technology. The photoinduced resistance is markedly decreased in the low temperature region (20-300 K), especially arresting at the T'C of o-YMnO3 (∼30 K), the T'N of o-YMnO3 (∼40 K), and the TN of h-YMnO3 (∼80 K). The variance tendency of the dielectric constant anomaly near the T'N of o-YMnO3 progressively decreases as the frequency increases, while the anomaly near the TN of h-YMnO3 is not observed in the same frequency region. Additionally, the dielectric constant is suppressed under photo excitation, and the variation increases with the rise in temperature and frequency. A distinct photoinduced suppression in the ferroelectric hysteresis loops is observed, maybe the trapping of photoinduced electrons to incur the reorientation of domain or increase the leakage current density. The obvious polarization switching in phase and amplitude images are observed when poling at ±8 V DC bias by the piezoresponse force microscopy technique at room temperature.