Modularization of Regional Electronic Structure over Defect-Rich CeO2 Rods for Enhancing Photogenerated Charge Transfer and CO2 Activation.

Oxygen vacancy (OV) engineering has been widely applied in different types of metal oxide-based photocatalytic reactions. Our study has shown that the redistributed OVs resulting from voids in CeO2 rods lead to significant differences in the band structure in space. The flat energy band within the highly crystallized bulk region hinders the recombination of photogenerated carrier pairs during the transfer process. The downward curved energy band in the surface region enhances the activation of the absorbents. Therefore, the localization of the band structure through crystal structure regionalization renders V-CeO2 capable of achieving efficient utilization of photogenerated carriers. Practically, the V-CeO2 rod shows a remarkable turnover number of 190.58 µmol g-1 h-1 in CO2 photoreduction, which is ∼9.4 times higher than that of D-CeO2 (20.46 µmol g-1 h-1). The designed modularization structure in our work is expected to provide important inspiration and guidance in coordinating the kinetic behavior of carriers in OV defect-rich photocatalysts.

Giant Deformation Induced Staggered-Layer Structure Promoting the Thermoelectric and Mechanical Performance in n-Type Bi2(Te, Se)3.

Bismuth telluride has long been recognized as the most promising near-room temperature thermoelectric material for commercial application; however, the thermoelectric performance for n-type Bi2(Te, Se)3-based alloys is far lagging behind that of its p-type counterpart. In this work, a giant hot deformation (GD) process is implemented in an optimized Bi2Te2.694Se0.3I0.006+3 wt%K2Bi8Se13 precursor and generates a unique staggered-layer structure. The staggered-layered structure, which is only observed in severely deformed crystals, exhibits a preferential scattering on heat-carrying phonons rather than charge-carrying electrons, thus resulting in an ultralow lattice thermal conductivity while retaining high-weight carrier mobility. Moreover, the staggered-layer structure is located adjacent to the van der Waals gap in Bi2(Te, Se)3 lattice and is able to strengthen the interaction between anion layers across the gap, leading to obviously improved compressive strength and Vickers hardness. Consequently, a high peak figure of merit ZT of ≈ 1.3 at 423 K, and an average ZT of ≈ 1.2 at 300-473 K can be achieved in GD sample. This study demonstrates that the GD process can successfully decouple the electrical and thermal transports with simultaneously enhanced mechanic performance.

Tuning the Electrolyte and Interphasial Chemistry for All-Climate Sodium-ion Batteries.

Sodium-ion batteries (SIBs) present a promising avenue for next-generation grid-scale energy storage. However, realizing all-climate SIBs operating across a wide temperature range remains a challenge due to the poor electrolyte conductivity and instable electrode interphases at extreme temperatures. Here, we propose a comprehensively balanced electrolyte by pairing carbonates with a low-freezing-point and low-polarity ethyl propionate solvent which enhances ion diffusion and Na+-desolvation kinetics at sub-zero temperatures. Furthermore, the electrolyte leverages a combinatorial borate- and nitrile-based additive strategy to facilitate uniform and inorganic-rich electrode interphases, ensuring excellent rate performance and cycle stability over a wide temperature range from -45 °C to 60 °C. Notably, the Na||sodium vanadyl phosphate cell delivers a remarkable capacity of 105 mAh g-1 with a high rate of 2 C at -25 °C. In addition, the cells exhibit excellent cycling stability over a wide temperature range, maintaining a high capacity retention of 84.7 % over 3,000 cycles at 60 °C and of 95.1 % at -25 °C over 500 cycles. The full cell also exhibits impressive cycling performance over a wide temperature range. This study highlights the critical role of electrolyte and interphase engineering for enabling SIBs that function optimally under diverse and extreme climatic environments.

Integrated energy storage and CO2 conversion using an aqueous battery with tamed asymmetric reactions.

Developing a CO2-utilization and energy-storage integrated system possesses great advantages for carbon- and energy-intensive industries. Efforts have been made to developing the Zn-CO2 batteries, but access to long cycling life and low charging voltage remains a grand challenge. Here we unambiguously show such inefficiencies originate from the high-barrier oxygen evolution reaction on charge, and by recharging the battery via oxidation of reducing molecules, Faradaic efficiency-enhanced CO2 reduction and low-overpotential battery regeneration can be simultaneously achieved. Showcased by using hydrazine oxidation, our battery demonstrates a long life over 1000 hours with a charging voltage as low as 1.2 V. The low charging voltage and formation of gaseous product upon hydrazine oxidation are the key to stabilize the catalyst over cycling. Our findings suggest that by fundamentally taming the asymmetric reactions, aqueous batteries are viable tools to achieve integrated energy storage and CO2 conversion that is economical, highly energy efficient, and scalable.

Rapid-charging aluminium-sulfur batteries operated at 85 °C with a quaternary molten salt electrolyte.

Molten salt aluminum-sulfur batteries are based exclusively on resourcefully sustainable materials, and are promising for large-scale energy storage owed to their high-rate capability and moderate energy density; but the operating temperature is still high, prohibiting their applications. Here we report a rapid-charging aluminium-sulfur battery operated at a sub-water-boiling temperature of 85 °C with a tamed quaternary molten salt electrolyte. The quaternary alkali chloroaluminate melt - possessing abundant electrochemically active high-order Al-Cl clusters and yet exhibiting a low melting point - facilitates fast Al3+ desolvation. A nitrogen-functionalized porous carbon further mediates the sulfur reaction, enabling the battery with rapid-charging capability and excellent cycling stability with 85.4% capacity retention over 1400 cycles at a charging rate of 1 C. Importantly, we demonstrate that the asymmetric sulfur reaction mechanism that involves formation of polysulfide intermediates, as revealed by operando X-ray absorption spectroscopy, accounts for the high reaction kinetics at such temperature wherein the thermal management can be greatly simplified by using water as the heating media.

Achieving Molecular-Level Selective Detection of Volatile Organic Compounds through a Strong Coupling Effect of Ultrathin Nanosheets and Au Nanoparticles.

The high density of surface active sites, high efficiency of interfacial carrier transport, and molecular diffusion path determine the efficiency of the electrochemical sensors. The ultrathin structures have atomic-level thickness, carrier migration and heat diffusion are limited in the two-dimensional plane, resulting in excellent conductivity and high carrier concentration. A one-step chemical method is applied to synthesize defect-rich Au-SnO2 in an ultrathin nanosheet form (thickness of 2-3 nm). The strong interaction between Au and SnO2 via the Au-O-Sn bonding and the catalytic effect of Au can prolong the service life via decreasing the optimal operating temperature (55 °C) and promote the Au-SnO2 sensor to exclusively detect formaldehyde at the ppb level (300 ppb). The experimental findings along with theoretical study reveal that Au nanoparticles have a different effect on the competitive adsorption and chemical reaction over the surface of the Au-SnO2 with formaldehyde and other interfering VOC gases, such as methanol, ethanol, and acetone. This study provides mechanistic insights into the correlation between operating temperature and the performance of the Au-SnO2 chemiresistive sensor. This work allows the development of highly efficient and stable electrochemical sensors to detect VOC gases at room temperature in the future.

Electrolyte Engineering with Tamed Electrode Interphases for High-Voltage Sodium-Ion Batteries.

Sodium-ion batteries (SIBs) hold great promise for next-generation grid-scale energy storage. However, the highly instable electrolyte/electrode interphases threaten the long-term cycling of high-energy SIBs. In particular, the instable cathode electrolyte interphase (CEI) at high voltage causes persistent electrolyte decomposition, transition metal dissolution, and fast capacity fade. Here, this work proposes a balanced principle for the molecular design of SIB electrolytes that enables an ultra-thin, homogeneous, and robust CEI layer by coupling an intrinsically oxidation-stable succinonitrile solvent with moderately solvating carbonates. The proposed electrolyte not only shows limited anodic decomposition thus leading to a thin CEI, but also suppresses dissolution of CEI components at high voltage. Consequently, the tamed electrolyte/electrode interphases enable extremely stable cycling of Na3V2O2(PO4)2F (NVOPF) cathodes with outstanding capacity retention (>90%) over 3000 cycles (8 months) at 1 C with a high charging voltage of 4.3 V. Further, the NVOPF||hard carbon full cell shows stable cycling over 500 cycles at 1 C with a high average Coulombic efficiency (CE) of 99.6%. The electrolyte also endows high-voltage operation of SIBs with great temperature adaptability from -25 to 60 °C, shedding light on the essence of fundamental electrolyte design for SIBs operating under harsh conditions.

Intrinsic surface p-wave superconductivity in layered AuSn4.

The search for topological superconductivity (TSC) is currently an exciting pursuit, since non-trivial topological superconducting phases could host exotic Majorana modes. However, the difficulty in fabricating proximity-induced TSC heterostructures, the sensitivity to disorder and stringent topological restrictions of intrinsic TSC place serious limitations and formidable challenges on the materials and related applications. Here, we report a new type of intrinsic TSC, namely intrinsic surface topological superconductivity (IS-TSC) and demonstrate it in layered AuSn4 with Tc of 2.4 K. Different in-plane and out-of-plane upper critical fields reflect a two-dimensional (2D) character of superconductivity. The two-fold symmetric angular dependences of both magneto-transport and the zero-bias conductance peak (ZBCP) in point-contact spectroscopy (PCS) in the superconducting regime indicate an unconventional pairing symmetry of AuSn4. The superconducting gap and surface multi-bands with Rashba splitting at the Fermi level (EF), in conjunction with first-principle calculations, strongly suggest that 2D unconventional SC in AuSn4 originates from the mixture of p-wave surface and s-wave bulk contributions, which leads to a two-fold symmetric superconductivity. Our results provide an exciting paradigm to realize TSC via Rashba effect on surface superconducting bands in layered materials.

Giant, Linearly Increasing Spin-Orbit Torque Efficiency in Symmetry-Broken Spin-Orbit Torque Superlattices.

Magnetic heterostructures with high spin-orbit torque efficiency and low impedance have great promise for low-power spintronic technologies. We report a symmetry-broken spin-orbit superlattice [Pt0.75Cu0.25/Co/Ta]n, in which the dampinglike spin-orbit torque efficiency accumulates linearly with the repeat number n and achieves a giant value of >200% when n = 16, which is 100 times stronger than that of a conventional magnetic heterostructure with a clean Pt (e.g., 2% at a resistivity of 7 µΩ cm). The giant spin-orbit torque effect arises predominantly from the spin Hall effect of Pt0.75Cu0.25. The anomalous Nernst effect increases remarkably as the repeat number n increases, implying a critical need to include the thermal effect in the analysis of magnetic superlattices and multilayers. The giant spin-orbit torque, low resistivity, and strong anomalous Nernst effect suggest the great potential of the superlattice [Pt0.75Cu0.25/Co/Ta]n for low-power memory and logic technologies as well as high-performance thermoelectric battery and sensor applications.

A solution-to-solid conversion chemistry enables ultrafast-charging and long-lived molten salt aluminium batteries.

Conventional solid-to-solid conversion-type cathodes in batteries suffer from poor diffusion/reaction kinetics, large volume changes and aggressive structural degradation, particularly for rechargeable aluminium batteries (RABs). Here we report a class of high-capacity redox couples featuring a solution-to-solid conversion chemistry with well-manipulated solubility as cathodes-uniquely allowed by using molten salt electrolytes-that enable fast-charging and long-lived RABs. As a proof-of-concept, we demonstrate a highly reversible redox couple-the highly soluble InCl and the sparingly soluble InCl3-that exhibits a high capacity of about 327 mAh g-1 with negligible cell overpotential of only 35 mV at 1 C rate and 150 °C. The cells show almost no capacity fade over 500 cycles at a 20 C charging rate and can sustain 100 mAh g-1 at 50 C. The fast oxidation kinetics of the solution phase upon initiating the charge enables the cell with ultrafast charging capability, whereas the structure self-healing via re-forming the solution phase at the end of discharge endows the long-term cycling stability. This solution-to-solid mechanism will unlock more multivalent battery cathodes that are attractive in cost but plagued by poor reaction kinetics and short cycle life.

Significantly Enhanced Thermoelectric Performance Achieved in CuGaTe2 through Dual-Element Permutations at Cation Sites.

CuGaTe2 has become a widely studied mid-temperature thermoelectric material due to the advantages of large element abundance, proper band gap, and intrinsically high Seebeck coefficient. However, the intrinsically high lattice thermal conductivity and low room-temperature electrical conductivity result in a merely moderate thermoelectric performance for pristine CuGaTe2. In this work, we found that Cu deficiency can significantly reduce the activation energy Ea of Cu vacancies from ∼0.17 eV for pristine CuGaTe2 to nearly zero for Cu0.97GaTe2, thus leading to dramatic improvements in hole concentration and power factor. More remarkably, element permutations (Ag/Cu and In/Ga) at both cation sites can effectively reduce the lattice thermal conductivity at the entire testing temperatures by producing intensive atomic-scale mass and strain fluctuations. Eventually, an ultrahigh peak ZTmax value of ∼1.5 at 873 K is achieved in the composition of Cu0.72Ag0.25Ga0.6In0.4Te2, while a large average ZTavg value of ∼0.7 (323-873 K) is obtained in the Cu0.67Ag0.3Ga0.6In0.4Te2 sample, both of which are significant improvements over pristine CuGaTe2.

Anchoring Platinum Clusters onto Oxygen Vacancy-Modified In2O3 for Ultraefficient, Low-Temperature, Highly Sensitive, and Stable Detection of Formaldehyde.

To avoid carcinogenicity, formaldehyde gas, currently being only detected at higher operating temperatures, should be selectively detected in time with ppb concentration sensitivity in a room-temperature indoor environment. This is achieved in this work through introducing oxygen vacancies and Pt clusters on the surface of In2O3 to reduce the optimal operating temperature from 120 to 40 °C. Previous studies have shown that only water participates in the competitive adsorption on the sensor surface. Here, we experimentally confirm that the adsorbed water on the fabricated sensor surface is consumed via a chemical reaction due to the strong interaction between the oxygen vacancies and Pt clusters. Therefore, the long-term stability of formaldehyde gas detection is improved. The results of theoretical calculations in this work reveal that the excellent formaldehyde gas detection of Pt/In2O3-x originates from the electron enrichment due to the surface oxygen vacancies and the molecular adsorption and activation ability of Pt clusters on the surface. The developed Pt/In2O3-x sensor has potential use in the ultraefficient, low-temperature, highly sensitive, and stable detection of indoor formaldehyde at an operating temperature as low as room temperature.

Air-Stable 2D Cr5 Te8 Nanosheets with Thickness-Tunable Ferromagnetism.

2D magnetic materials have aroused widespread research interest owing to their promising application in spintronic devices. However, exploring new kinds of 2D magnetic materials with better stability and realizing their batch synthesis remain challenging. Herein, the synthesis of air-stable 2D Cr5 Te8 ultrathin crystals with tunable thickness via tube-in-tube chemical vapor deposition (CVD) growth technology is reported. The importance of tube-in-tube CVD growth, which can significantly suppress the equilibrium shift to the decomposition direction and facilitate that to the synthesis reaction direction, for the synthesis of high-quality Cr5 Te8 with accurate composition, is highlighted. By precisely adjusting the growth temperature, the thickness of Cr5 Te8 nanosheets is tuned from ≈1.2 nm to tens of nanometers, with the morphology changing from triangles to hexagons. Furthermore, magneto-optical Kerr effect measurements reveal that the Cr5 Te8 nanosheet is ferromagnetic with strong out-of-plane spin polarization. The Curie temperature exhibits a monotonic increase from 100 to 160 K as the Cr5 Te8 thickness increases from 10 to 30 nm and no apparent variation in surface roughness or magnetic properties after months of exposure to air. This study provides a robust method for the controllable synthesis of high-quality 2D ferromagnetic materials, which will facilitate research progress in spintronics.

Fully Spin-Transparent Magnetic Interfaces Enabled by the Insertion of a Thin Paramagnetic NiO Layer.

Spin backflow and spin-memory loss have been well established to considerably lower the interfacial spin transmissivity of metallic magnetic interfaces and thus the energy efficiency of spin-orbit torque technologies. Here, we report that spin backflow and spin-memory loss at Pt-based heavy metal-ferromagnet interfaces can be effectively eliminated by inserting an insulating paramagnetic NiO layer of optimum thickness. The latter enables the thermal magnon-mediated essentially unity spin-current transmission at room temperature due to considerably enhanced effective spin-mixing conductance of the interface. As a result, we obtain dampinglike spin-orbit torque efficiency per unit current density of up to 0.8 as detected by the standard technology ferromagnet FeCoB and others, which reaches the expected upper-limit spin Hall ratio of Pt. We establish that Pt/NiO and Pt-Hf/NiO are two energy-efficient, integration-friendly, and high-endurance spin-current generators that provide >100 times greater energy efficiency than sputter-deposited topological insulators BiSb and BiSe. Our finding will benefit spin-orbitronic research and advance spin-torque technologies.

Variation of the giant intrinsic spin Hall conductivity of Pt with carrier lifetime.

More than a decade after the first theoretical and experimental studies of the spin Hall conductivity (SHC) of Pt, both its dominant origin and amplitude remain in dispute. We report the experimental determination of the rapid variation of the intrinsic SHC of Pt with the carrier lifetime (τ) in the dirty-metal regime by incorporating finely dispersed MgO intersite impurities into the Pt, while maintaining its essential band structure. This conclusively validates the theoretical prediction that the SHC in Pt in the dirty-metal regime should be dominated by the intrinsic contribution, and should decrease rapidly with shortening τ. When interfacial spin backflow is taken into account, the intrinsic SHC of Pt in the clean limit is at least 1.6 × 106 (ℏ/2e) ohm-1 m-1, more than 3.5 times greater than the available theoretical predictions. Our work also establishes a compelling spin Hall metal Pt0.6(MgO)0.4 with an internal giant spin Hall ratio of 0.73.

Dimension Engineering of High-Quality InAs Nanostructures on a Wafer Scale.

Low-dimensional narrow-band-gap III-V semiconductors are key building blocks for the next generation of high-performance nanoelectronics, nanophotonics, and quantum devices. Realizing these various applications requires an efficient methodology that enables the material dimensional control during the synthesis process and the mass production of these materials with perfect crystallinity, reproducibility, low cost, and outstanding electronic and optoelectronic properties. Although advances in one- and two-dimensional narrow-band-gap III-V semiconductors synthesis, the progress toward reliable methods that can satisfy all of these requirements has been limited. Here, we demonstrate an approach that provides a precise control of the dimension of InAs from one-dimensional nanowires to wafer-scale free-standing two-dimensional nanosheets, which have a high degree of crystallinity and outstanding electrical and optical properties, using molecular-beam epitaxy by controlling catalyst alloy segregation. In our approach, two-dimensional InAs nanosheets can be obtained directly from one-dimensional InAs nanowires by silver-indium alloy segregation, which is much easier than the previously reported methods, such as the traditional buffering technique and select-area epitaxial growth. Detailed transmission electron microscopy investigations provide solid evidence that the catalyst alloy segregation is the origination of the InAs dimensional transformation from one-dimensional nanowires to two-dimensional nanosheets and even to three-dimensional complex crosses. Using this method, we find that the wafer-scale free-standing InAs nanosheets can be grown on various substrates including Si, MgO, sapphire, GaAs, etc. The InAs nanosheets grown at high temperature are pure-phase single crystals and have a high electron mobility and a long time-resolved terahertz kinetics lifetime. Our work will open up a conceptually new and general technology route toward the effective controlling of the dimension of the low-dimensional III-V semiconductors. It may also enable the low-cost fabrication of free-standing nanosheet-based devices on an industrial scale.