Surface-Enriched Room-Temperature Liquid Bismuth for Catalytic CO2 Reduction.

Bismuth-based electrocatalysts are effective for carbon dioxide (CO2) reduction to formate. However, at room temperature, these materials are only available in solid state, which inevitably suffers from surface deactivation, declining current densities, and Faradaic efficiencies. Here, the formation of a liquid bismuth catalyst on the liquid gallium surface at ambient conditions is shown as its exceptional performance in the electrochemical reduction of CO2 (i.e., CO2RR). By doping a trace amount of bismuth (740 ppm atomic) in gallium liquid metal, a surface enrichment of bismuth by over 400 times (30 at%) in liquid state is obtained without atomic aggregation, achieving 98% Faradic efficiency for CO2 conversion to formate over 80 h. Ab initio molecular simulations and density functional theory calculations reveal that bismuth atoms in the liquid state are the most energetically favorable sites for the CO2RR intermediates, superior to solid Bi-sites, as well as joint GaBi-sites. This study opens an avenue for fabricating high-performing liquid-state metallic catalysts that cannot be reached by elementary metals under electrocatalytic conditions.

Effect of Fe Doping Profile on Current Collapse in GaN-based RF HEMTs.

Using computer-aided design (TCAD) simulation, the impact of the Fe doping profile, including concentration, decay rate, and depth of the doping region on current-collapse magnitude (▵CC) in 0.5-µm gated GaN-based high electron mobility transistors (HEMTs) is systematically investigated. Accurate simulation models are established and developed to facilitate the fabrication of electronics. It is elucidated that the intricate interplay between trapping and de-trapping of Fe-related traps at the gate-drain edge is responsible for current collapse. The concentration and decay rate of the doping region have a more significant impact on current collapse than the depth. Increased trap state density near two-dimensional electron gas (2DEG) channel caused by deep-level acceptors would boost ▵CC. However, a minor dynamic reduction in 2DEG density (nT) induces a relatively small ▵CC. By adjusting the concentration, decay rate, and depth of the doping region, ▵CC of GaN-based Radio Frequency (RF) HEMTs can be reduced by approximately 50.3 %. The optimized distribution of Fe doping discussed in this work helps to prepare GaN-based RF HEMTs with a limited current collapse effect.

Multi-Scale Dispersion Engineering on Biomass-Derived Materials for Ultra-Wideband and Wide-Angle Microwave Absorption.

Efficient electromagnetic waves (EMWs) absorbing materials play a vital role in the electronic era. In traditional research on microwave absorbing (MA) materials, the synergistic modulation of material dispersion and structural dispersion of EMWs by incorporating multi-scale effects has frequently been overlooked, resulting in an untapped absorption potential. In this study, the material dispersion customization method based on biomass carbon is determined by quantitative analysis. The study carries out thermodynamic modulation of carbon skeleton, micro-nano porous engineering, and phosphorus atom donor doping in turn. The dielectric properties are improved step by step. In terms of structural dispersion design, inspired by the theory of antenna reciprocity, a Vivaldi antenna-like absorber is innovatively proposed. With the effective combination of material dispersion and structural dispersion engineering by 3D printing technology, the ultra-wideband absorption of 36.8 GHz and the angular stability of close to 60 ° under dual polarization are successfully realized. The work breaks the deadlock of mutual constraints between wave impedance and attenuation rate through the dispersion modulation methods on multiple scales, unlocking the potential for designing next-generation broadband wide-angle absorbers.

Fluorescent Nanocarbons: From Synthesis and Structure to Cancer Imaging and Therapy.

Nanocarbons are emerging at the forefront of nanoscience, with diverse carbon nanoforms emerging over the past two decades. Early cancer diagnosis and therapy, driven by advanced chemistry techniques, play a pivotal role in mitigating mortality rates associated with cancer. Nanocarbons, with an attractive combination of well-defined architectures, biocompatibility, and nanoscale dimension, offer an incredibly versatile platform for cancer imaging and therapy. This paper aims to review the underlying principles regarding the controllable synthesis, fluorescence origins, cellular toxicity, and surface functionalization routes of several classes of nanocarbons: carbon nanodots, nanodiamonds, carbon nanoonions, and carbon nanohorns. This review also highlights recent breakthroughs regarding the green synthesis of different nanocarbons from renewable sources. It also presents a comprehensive and unified overview of the latest cancer-related applications of nanocarbons and how they can be designed to interface with biological systems and work as cancer diagnostics and therapeutic tools. The commercial status for large-scale manufacturing of nanocarbons is also presented. Finally, it proposes future research opportunities aimed at engendering modifiable and high-performance nanocarbons for emerging applications across medical industries. This work is envisioned as a cornerstone to guide interdisciplinary teams in crafting fluorescent nanocarbons with tailored attributes that can revolutionize cancer diagnostics and therapy.

Liquid Metal Doping Induced Asymmetry in Two-Dimensional Metal Oxides.

The emergence of ferroelectricity in two-dimensional (2D) metal oxides is a topic of significant technological interest; however, many 2D metal oxides lack intrinsic ferroelectric properties. Therefore, introducing asymmetry provides access to a broader range of 2D materials within the ferroelectric family. Here, the generation of asymmetry in 2D SnO by doping the material with Hf0.5 Zr0.5 O2 (HZO) is demonstrated. A liquid metal process as a doping strategy for the preparation of 2D HZO-doped SnO with robust ferroelectric characteristics is implemented. This technology takes advantage of the selective interface enrichment of molten Sn with HZO crystallites. Molecular dynamics simulations indicate a strong tendency of Hf and Zr atoms to migrate toward the surface of liquid metal and embed themselves within the growing oxide layer in the form of HZO. Thus, the liquid metal-based harvesting/doping technique is a feasible approach devised for producing novel 2D metal oxides with induced ferroelectric properties, represents a significant development for the prospects of random-access memories.

Nitrogen rejection in natural gas using NaZSM-25 zeolite.

Natural gas reservoirs usually contain considerable amounts of nitrogen (N2). Methane (CH4) as the main component in natural gas must be purified before transferring to the pipeline or storing as liquified natural gas (LNG). Currently, energy-intensive cryogenic distillation is the only industrial approach for N2 rejection in natural gas. The adsorption process based on a N2-selective adsorbent can minimize the separation cost. However, the search for an adsorbent that can selectively reject N2 in natural gas has lasted for decades. Here, we report a microporous zeolite called NaZSM-25 capable of adsorbing N2 over CH4 with an exceptional selectivity of 47 at room temperature that outperforms all previously known N2-selective adsorbents. At 295 K and 100 kPa, the N2 and CH4 uptakes on NaZSM-25 were 0.25 and 0.005 mmol g-1, respectively. CH4 showed negligible external surface adsorption in the whole temperature range of 273-323 K. Theoretical studies through replica exchanged Monte Carlo, molecular dynamics, and ab initio density functional theory (DFT) proved the diffusion limitation of CH4 as a result of 8-membered ring (8MR) pore opening deformation by Na+ cation. The DFT results showed the diffusion energy barriers of 63 and 96 kJ mol-1 for N2 and CH4, respectively, when passing an 8MR occupied with a Na+. NaZSM-25 is a promising adsorbent to be utilized in a pressure swing adsorption process at room temperature to minimize the energy consumption in N2 rejection units.

Facile Fabrication of Monodispersed Carbon Sphere: A Pathway Toward Energy-Efficient Direct Air Capture (DAC) Using Amino Acids.

Direct removal of carbon dioxide (CO2 ) from the atmosphere, known as direct air capture (DAC) is attracting worldwide attention as a negative emission technology to control atmospheric CO2 concentrations. However, the energy-intensive nature of CO2 absorption-desorption processes has restricted deployment of DAC operations. Catalytic solvent regeneration is an effective solution to tackle this issue by accelerating CO2 desorption at lower regeneration temperatures. This work reports a one-step synthesis methodology to prepare monodispersed carbon nanospheres (MCSs) using trisodium citrate as a structure-directing agent with acidic sites. The assembly of citrate groups on the surface of MCSs enables consistent spherical growth morphology, reduces agglomeration and enhances water dispersibility. The functionalization-assisted synthesis produces uniform, hydrophilic nanospheres of 100-600 nm range. This work also demonstrates that the prepared MCSs can be further functionalized with strong Brønsted acid sites, providing high proton donation ability. Furthermore, the materials can be effectively used in a wide range of amino acid solutions to substantially accelerate CO2 desorption (25.6% for potassium glycinate and 41.1% for potassium lysinate) in the DAC process. Considering the facile synthesis of acidic MCSs and their superior catalytic efficiency, these findings are expected to pave a new path for energy-efficient DAC.

Coating of gallium-based liquid metal particles with molybdenum oxide and oxysulfide for electronic band structure modulation.

Liquid metal (LM) droplets are now used in many applications including catalysis, sensing, and flexible electronics. Consequently, the introduction of methods for on-demand alternating electronic properties of LMs is necessary. The active surface of LMs provides a unique environment for spontaneous chemical reactions that enable the formation of thin layers of functional materials for such modulations. Here, we showed the deposition of n-type MoOx and MoOxSy semiconductors on the surface of EGaIn LM droplets under mechanical agitation to successfully modulate their electronic structures. The "liquid solution"-"liquid metal" interaction resulted in the formation of oxide and oxysulfide layers on the surface of LM droplets. The comprehensive study of electronic and optical properties revealed a decrease in the band gap of the droplets after surface decoration with MoOx and MoOxSy, leading to deeper n-type doping of the materials. This method provides a facile procedure for engineering the electronic band structure of LM-based composites when they are necessary for various applications.

Gas sensors based on the oxide skin of liquid indium.

Various non-stratified two-dimensional (2D) materials can be obtained from liquid metal surfaces that are not naturally accessible. Homogenous nucleation on atomically flat interfaces of liquid metals with air produces unprecedented high-quality oxide layers that can be transferred onto desired substrates. The atomically flat and large areas provide large surface-to-volume ratios ideal for sensing applications. Versatile crucial applications of the liquid metal-derived 2D oxides have been realized; however, their gas-sensing properties remain largely underexplored. The cubic In2O3 structure, which is nonlayered, can be formed as an ultrathin layer on the surface of liquid indium during the self-limiting Cabrera-Mott oxidation process in the air. The morphology, crystal structure, and band structure of the harvested 2D In2O3 nanosheets from liquid indium are characterized. Sensing capability toward several gases, both inorganic and organic, entailing NO2, O2, NH3, H2, H2S, CO, and Methyl ethyl ketone (MEK) are explored. A high ohmic resistance change of 1974% at 10 ppm, fast response, and recovery times are observed for NO2 at an optimum temperature of 200 °C. The sensing fundamentals are investigated for NO2, and its performances and cross-selectivity to different gases are analyzed. The NO2 sensing response from room temperature to 300 °C has been measured and discussed, and stability after 24 hours of continuous operation is presented. The results demonstrate liquid metal-derived 2D oxides as promising materials for gas sensing applications.

Nitrogen-Doped Porous Nickel Molybdenum Phosphide Sheets for Efficient Seawater Splitting.

Hydrogen is emerging as an alternative clean fuel; however, its dependency on freshwater will be a threat to a sustainable environment. Seawater, an unlimited source, can be an alternative, but its salt-rich nature causes corrosion and introduces several competing reactions, hindering its use. To overcome these, a unique catalyst composed of porous sheets of nitrogen-doped NiMo3 P (N-NiMo3 P) having a sheet size of several microns is designed. The presence of large homogenous pores in the basal plane of these sheets makes them catalytically more active and ensures faster mass transfer. The introduction of N and Ni into MoP significantly tunes the electronic density of Mo, surface chemistry, and metal-non-metal bond lengths, optimizing surface energies, creating new active sites, and increasing electrical conductivity. The presence of metal-nitrogen bonds and surface polyanions increases the stability and improves anti-corrosive properties against chlorine chemistry. Ultimately, the N-NiMo3 P sheets show remarkable performance as it only requires overpotentials of 23 and 35 mV for hydrogen evolution reaction, and it catalyzes full water splitting at 1.52 and 1.55 V to achieve 10 mA cm-2 in 1 m KOH and seawater, respectively. Hence, structural and compositional control can make catalysts effective in realizing low-cost hydrogen directly from seawater.

Screening of Alkali Metal-Exchanged Zeolites for Nitrogen/Methane Separation.

Methane (CH4) is the primary component of natural gas and must be purified to a certain level before it can be used as pipeline gas or liquified natural gas (LNG). In particular, nitrogen (N2), a common contaminant in natural gas needs to be rejected to increase the heating value of the gas and meet the LNG product specifications. The development of energy-efficient N2 removal technologies is hampered by N2's inertness and its resemblance to CH4 in terms of kinetic size and polarizability. N2-selective materials are so rare. Here, for the first time, we screened 1425 alkali metal cation exchange zeolites to identify the candidates with the best potential for the separation of N2 from CH4. We discovered a few extraordinary zeolite frameworks capable of achieving equilibrium selectivity toward N2. Particularly, Li+-RRO-3 zeolite with a specific two-dimensional structure demonstrated a selective N2 adsorption capacity of 2.94 mmol/g at 283 K and 1 bar, outperforming the capacity of all known zeolites. Through an ab initio density functional theory study, we found that the five-membered ring of the RRO framework is the most stable cationic site for Li+, and this Li+ can interact with multiple N2 molecules but only one CH4, revealing the mechanism for the high capacity and selectivity of N2. This work suggests promising adsorbents to enable N2 rejection from CH4 in the gas industry without going for energy-intensive cryogenic distillations.

Nanobionics-Driven Synthesis of Molybdenum Oxide Nanosheets with Tunable Plasmonic Resonances in Visible Light Regions.

Nanobionics-driven synthesis offers a process of designing and synthesizing functional materials on a nanoscale based on the structures and functions of biological systems. An approach such as this is environmentally friendly and sustainable, providing a viable option for synthesizing functional nanomaterials for catalysis and nanoelectronic components. In this work, we present a facile and green nanobionics approach to synthesize plasmonic HxMoO3 by interacting chloroplasts extracted from spinach with two-dimensional (2D) MoO3 nanoflakes. The generated plasmon resonances can be modulated in the visible wavelength ranges, and the efficiency to form the plasmonic materials is enhanced by 90% within 45 min of light excitation compared to reactions without chloroplast involvement. Such a characteristic is ascribed to the interfacial carrier dynamics between the two entities in the reactions, in which highly doped metal oxides with quasi-metallic properties can be formed to generate optical absorptions in the visible light region. The green synthesized plasmonic materials show high photocatalytic activities without the coupling of semiconductors, providing a promising nanoelectronics unit, based on the nanobionics-driven synthesized plasmonic materials.

Hydrogen production from the air.

Green hydrogen produced by water splitting using renewable energy is the most promising energy carrier of the low-carbon economy. However, the geographic mismatch between renewables distribution and freshwater availability poses a significant challenge to its production. Here, we demonstrate a method of direct hydrogen production from the air, namely, in situ capture of freshwater from the atmosphere using hygroscopic electrolyte and electrolysis powered by solar or wind with a current density up to 574 mA cm-2. A prototype of such has been established and operated for 12 consecutive days with a stable performance at a Faradaic efficiency around 95%. This so-called direct air electrolysis (DAE) module can work under a bone-dry environment with a relative humidity of 4%, overcoming water supply issues and producing green hydrogen sustainably with minimal impact to the environment. The DAE modules can be easily scaled to provide hydrogen to remote, (semi-) arid, and scattered areas.

Doped 2D SnS materials derived from liquid metal-solution for tunable optoelectronic devices.

Gas-liquid reaction phenomena on liquid-metal solvents can be used to form intriguing 2D materials with large lateral dimensions, where the free energies of formation determine the final product. A vast selection of elements can be incorporated into the liquid metal-based nanostructures, offering a versatile platform for fabricating novel optoelectronic devices. While conventional doping techniques of semiconductors present several challenges for 2D materials. Liquid metals provide a facile route for obtaining doped 2D semiconductors. In this work, we successfully demonstrate that the doping of 2D SnS can be realized in a glove box containing a diluted H2S gas. Low melting point elements such as Bi and In are alloyed with base liquid Sn in varying concentrations, resulting in the doping of 2D SnS layers incorporating Bi and In sulphides. Optoelectronic properties for photodetectors and piezoelectronics can be fine-tuned through the controlled introduction of selective migration doping. The structural modification of 2D SnS results in a 22.6% enhancement of the d11 piezoelectric coefficient. In addition, photodetector response times have increased by several orders of magnitude. Doping methods using liquid metals have significantly changed the photodiode and piezoelectric device performances, providing a powerful approach to tune optoelectronic device outputs.

Large Area Ultrathin InN and Tin Doped InN Nanosheets Featuring 2D Electron Gases.

Indium nitride (InN) has been of significant interest for creating and studying two-dimensional electron gases (2DEG). Herein we demonstrate the formation of 2DEGs in ultrathin doped and undoped 2D InN nanosheets featuring high carrier mobilities at room temperature. The synthesis is carried out via a two-step liquid metal-based printing method followed by a microwave plasma-enhanced nitridation reaction. Ultrathin InN nanosheets with a thickness of ∼2 ± 0.2 nm were isolated over large areas with lateral dimensions exceeding centimeter scale. Room temperature Hall effect measurements reveal carrier mobilities of ∼216 and ∼148 cm2 V-1 s-1 for undoped and doped InN, respectively. Further analysis suggests the presence of defined quantized states in these ultrathin nitride nanosheets that can be attributed to a 2D electron gas forming due to strong out-of-plane confinement. Overall, the combination of electronic and plasmonic features in undoped and doped ultrathin 2D InN holds promise for creating advanced optoelectronic devices and functional 2D heterostructures.

Electrical Regulation of CO2 Adsorption in the Metal-Organic Framework MIL-53.

Active regulation of pore accessibility in microporous materials by external stimuli has aroused great attention in recent years. Here, we show the first experimental proof that guest adsorption in a dielectric microporous material can be regulated by a moderate external E-field below the gas breakdown voltage. CO2 adsorption capacity in MIL-53 (Al) was significantly reduced, whereas that of NH2-MIL-53 (Al) changed insignificantly under a direct current E-field gradient of 286 V/mm. Ab initio DFT calculations revealed that the E-field decreased the charge transfer between the CO2 molecule and the adsorption site in the MIL-53 framework, which resulted in reduced binding energy and consequently lowered CO2 adsorption capacity. This effect was only observed in the narrow pore state MIL-53 (Al) but not in its large pore configuration. Our results demonstrate the feasibility of regulating the adsorption of gas molecules in microporous materials using moderate E-fields.

Engineered assembly of water-dispersible nanocatalysts enables low-cost and green CO2 capture.

Catalytic solvent regeneration has attracted broad interest owing to its potential to reduce energy consumption in CO2 separation, enabling industry to achieve emission reduction targets of the Paris Climate Accord. Despite recent advances, the development of engineered acidic nanocatalysts with unique characteristics remains a challenge. Herein, we establish a strategy to tailor the physicochemical properties of metal-organic frameworks (MOFs) for the synthesis of water-dispersible core-shell nanocatalysts with ease of use. We demonstrate that functionalized nanoclusters (Fe3O4-COOH) effectively induce missing-linker deficiencies and fabricate mesoporosity during the self-assembly of MOFs. Superacid sites are created by introducing chelating sulfates on the uncoordinated metal clusters, providing high proton donation capability. The obtained nanomaterials drastically reduce the energy consumption of CO2 capture by 44.7% using only 0.1 wt.% nanocatalyst, which is a ∽10-fold improvement in efficiency compared to heterogeneous catalysts. This research represents a new avenue for the next generation of advanced nanomaterials in catalytic solvent regeneration.

Liquid metals: an ideal platform for the synthesis of two-dimensional materials.

The surfaces of liquid metals can serve as a platform to synthesise two-dimensional materials. By exploiting the self-limiting Cabrera-Mott oxidation reaction that takes place at the surface of liquid metals exposed to ambient air, an ultrathin oxide layer can be synthesised and isolated. Several synthesis approaches based on this phenomenon have been developed in recent years, resulting in a diverse family of functional 2D materials that covers a significant fraction of the periodic table. These straightforward and inherently scalable techniques may enable the fabrication of novel devices and thus harbour significant application potential. This review provides a brief introduction to liquid metals and their alloys, followed by detailed guidance on each developed synthesis technique, post-growth processing methods, integration processes, as well as potential applications of the developed materials.

Formation of a Stable Surface Oxide in MnBi2Te4 Thin Films.

Understanding the air stability of MnBi2Te4 thin films is crucial for the development and long-term operation of electronic devices based on magnetic topological insulators. In the present work, we study MnBi2Te4 thin films upon exposure to the atmosphere using a combination of synchrotron-based photoelectron spectroscopy, room-temperature electrical transport, and atomic force microscopy to determine the oxidation process. After 2 days of air exposure, a 2 nm thick oxide passivates the surface, corresponding to the oxidation of only the top two surface layers, with the underlying layers preserved. This protective oxide layer results in samples that still exhibit metallic conduction even after several days of air exposure. Furthermore, the work function decreases from 4.4 eV for pristine MnBi2Te4 to 4.0 eV after the formation of the oxide, along with only a small shift in the core levels, indicating minimal doping as a result of air exposure. With the oxide confined to the top surface layers, and the underlying layers preserved, it may be possible to explore new avenues in how to handle, prepare, and passivate future MnBi2Te4 devices.

Liquid metal derived MOF functionalized nanoarrays with ultra-wideband electromagnetic absorption.

Low melting point liquid metal alloys are progressively utilized in different research fields due to their unique physicochemical properties. Among them, EGaIn is liquid at room temperature with an excellent solubility for reactive metal atoms such as Al. Combined with their characteristic flexible surface, large area and atomically flat interfaces, a library of two-dimensional materials can be generated. Liquid metal synthesis routes provide a highly reproducible thickness of nanosheets with fast, simple, scalable, inexpensive, high yield and non-toxic methods, especially for Al oxides and hydroxides. At the same time, Al-based heterojunction structure also shows a good application prospect in the field of electromagnetic wave absorption, therefore, the use of liquid metal synthesis methods to find the synthesis methods of Al-based layered double hydroxide (LDH) and its derivatives remains to be explored. In this work, EGaIn was used as an aluminum reservoir to prepare LDH and metal organic framework (MOFs) nano-arrays. The prepared CoAl-LDH@ZIF 67 can be transformed into CoAl-LDO@Co-C in the subsequent annealing process performed under nitrogen environments. Interestingly, a series of samples with different morphologies can be obtained by changing the synthesis parameters. The excellent electromagnetic wave interactions are fully characterized. It has an effective absorption bandwidth of 8.48 GHz at 2.6 mm. The findings demonstrated in this work pave the way for the application of lightwave and ductile complex nanoarrays obtained from liquid metals.