Comparison of copper and graphene-assembled films in 5G wireless communication and THz electromagnetic-interference shielding.

Since first developed, the conducting materials in wireless communication and electromagnetic interference (EMI) shielding devices have been primarily made of metal-based structures. Here, we present a graphene-assembled film (GAF) that can be used to replace copper in such practical electronics. The GAF-based antennas present strong anticorrosive behavior. The GAF ultra-wideband antenna covers the frequency range of 3.7 GHz to 67 GHz with the bandwidth (BW) of 63.3 GHz, which exceed ~110% than the copper foil-based antenna. The GAF Fifth Generation (5G) antenna array features a wider BW and lower sidelobe level compared with that of copper antennas. EMI shielding effectiveness (SE) of GAF also outperforms copper, reaching up to 127 dB in the frequency range of 2.6 GHz to 0.32 THz, with a SE per unit thickness of 6,966 dB/mm. We also confirm that GAF metamaterials exhibit promising frequency selection characteristics and angular stability as flexible frequency selective surfaces.

Accelerating the Hydrogen Production via Modifying the Fermi Surface.

The design of catalysts has attracted a great deal of attention in the field of electrocatalysis. The accurate design of the catalysts can avoid an unnecessary process that occurs during the blind trial. Based on the interaction between different metal species, a metallic compound supported by the carbon nanotube was designed. Among these compounds, RhFeP2CX (R-RhFeP2CX-CNT) was found to be in a rich-electron environment at the Fermi level (denoted as a flat Fermi surface), beneficial to the hydrogen evolution reaction (HER). R-RhFeP2CX-CNT exhibits a small overpotential of 15 mV at the current density of 10 mA·cm-2 in acidic media. Moreover, the mass activity of R-RhFeP2CX-CNT is 21597 A·g-1, which also demonstrates the advance of the active sites on R-RhFeP2CX-CNT. Therefore, R-RhFeP2CX-CNT can be an alternative catalyst applied in practical production, and the strategies of a flat Fermi surface will be a reliable strategy for catalyst designing.

Hybrid dual-mode tunable polarization conversion metasurface based on graphene and vanadium dioxide.

We present and numerically verify a functionally hybrid dual-mode tunable polarization conversion metasurface based on graphene and vanadium dioxide (VO2). The tunable polarization converter consists of two patterned graphene layers separated by grating which is composed of gold and VO2. Due to the existence of phase change material VO2, the polarization conversion mode can be switched flexibly between the transmission and reflection modes. Theoretical calculations show the proposed polarization conversion metasurface can obtain giant asymmetric transmission (AT) at 0.42 and 0.77 THz when VO2 is in the insulating state. Conversely, when VO2 is in the metallic state, the converter switches to the reflection mode, demonstrating broadband polarization conversion for both forward and backward incidences. Furthermore, the conductivity of graphene can be modulated by changing the gate voltage, which allows dynamic control polarization conversion bandwidth of the reflection mode as well as the AT of the transmission mode. The robustness of the metasurface has also been verified, the high polarization conversion efficiency and AT can be maintained over wide incidence angles up to 65° for both the xoz plane and yoz plane. These advantages make the proposed hybrid tunable polarization conversion metasurface a promising candidate for THz radiation switching and modulation.

Aqueous MXene/Xanthan Gum Hybrid Inks for Screen-Printing Electromagnetic Shielding, Joule Heater, and Piezoresistive Sensor.

MXenes have exhibited potential for application in flexible devices owing to their remarkable electronic, optical, and mechanical properties. Printing strategies have emerged as a facile route for additive manufacturing of MXene-based devices, which relies on the rational design of functional inks with appropriate rheological properties. Herein, aqueous MXene/xanthan gum hybrid inks with tunable viscosity, excellent printability, and long-term stability are designed. Screen-printed flexible MXene films using such hybrid inks exhibit a high conductivity up to 4.8 × 104  S m-1 , which is suitable to construct multifunctional devices mainly including electromagnetic shielding, Joule heaters, and piezoresistive sensors. The average electromagnetic interference (EMI) shielding value can reach to 40.1 dB. In the Joule heater, the heating rate of printed MXene film can reach 20 °C s-1 under a driving voltage of 4 V, with a highest steady-state temperature of 130.8 °C. An MXene-based piezoresistive sensor prepared by the printing interdigital electrode also presents good sensing performance with a short response time of 130 ms and wide pressure region up to 30 kPa. As a result, screen-printed MXene film exhibits reinforced multifunctional performance, which is promising for application in the next-generation of intelligent and wearable devices.

Ternary Alloys Enable Efficient Production of Methoxylated Chemicals via Selective Electrocatalytic Hydrogenation of Lignin Monomers.

We explore the selective electrocatalytic hydrogenation of lignin monomers to methoxylated chemicals, of particular interest, when powered by renewable electricity. Prior studies, while advancing the field rapidly, have so far lacked the needed selectivity: when hydrogenating lignin-derived methoxylated monomers to methoxylated cyclohexanes, the desired methoxy group (-OCH3) has also been reduced. The ternary PtRhAu electrocatalysts developed herein selectively hydrogenate lignin monomers to methoxylated cyclohexanes-molecules with uses in pharmaceutics. Using X-ray absorption spectroscopy and in situ Raman spectroscopy, we find that Rh and Au modulate the electronic structure of Pt and that this modulating steers intermediate energetics on the electrocatalyst surface to facilitate the hydrogenation of lignin monomers and suppress C-OCH3 bond cleavage. As a result, PtRhAu electrocatalysts achieve a record 58% faradaic efficiency (FE) toward 2-methoxycyclohexanol from the lignin monomer guaiacol at 200 mA cm-2, representing a 1.9× advance in FE and a 4× increase in partial current density compared to the highest productivity prior reports. We demonstrate an integrated lignin biorefinery where wood-derived lignin monomers are selectively hydrogenated and funneled to methoxylated 2-methoxy-4-propylcyclohexanol using PtRhAu electrocatalysts. This work offers an opportunity for the sustainable electrocatalytic synthesis of methoxylated pharmaceuticals from renewable biomass.

Sulfate Ions Induced Concave Porous S-N Co-Doped Carbon Confined FeCx Nanoclusters with Fe-N4 Sites for Efficient Oxygen Reduction in Alkaline and Acid Media.

To improve the catalytic activity of the catalysts, it is key to intensifying the intrinsic activity of active sites or increasing the exposure of accessible active sites. In this work, an efficient oxygen reduction electrocatalyst is designed that confines plentiful FeCx nanoclusters with Fe-N4 sites in a concave porous S-N co-doped carbon matrix, readily accessible for the oxygen reduction reaction (ORR). Sulfate ions react with the carbon derived from ZIF-8 at high temperatures, leading to the shrinkage of the carbon framework and then forming a concave structure with abundant macropores and mesopores with S incorporation. Such an architecture promotes the exposure of active sites and accelerates remote mass transfer. As a result, the catalyst (Fe/S-NC) with a large number of C-S-C, Fe-N4 , and FeCx nanoclusters presents impressive ORR activity and stability. In alkaline media, the half-wave potential of the best catalyst (Fe/S2 -NC) is 0.91 V, which far exceeds that of commercial platinum carbon (0.85 V), while in acidic media the half-wave potential reaches 0.784 V, comparable to platinum carbon (0.812 V). Furthermore, for the zinc-air battery, the outstanding peak power density of Fe/S2 -NC (170 mW cm-2 ) superior to platinum carbon (108 mW cm-2 ) also highlights its great application potential.

Hybrid metamaterial absorber for ultra-low and dual-broadband absorption.

Developing high-efficiency microwave absorbers remains challenging in the broadband range, particularly in the low-frequency range containing the L band and even lower. To overcome this challenge, a hybrid metamaterial absorber comprising a conventional magnetic absorbing material and a multi-layered meta-structure predesigned with graphene films is proposed to realize wideband absorption performance starting from ultra-low frequencies (0.79-20.9 GHz and 25.1-40.0 GHz). The high absorption ability of the proposed device originates from fundamental resonance modes and their coupling. The experimental results agree well with the simulated ones, proving the effectiveness of our design method. In addition, owing to the use of low-density polymethylacrylimide foam and graphene films with outstanding mechanical properties, our design is lightweight and environmentally adaptable, which reflects its engineering value.

Flexible Anti-Metal RFID Tag Antenna Based on High-Conductivity Graphene Assembly Film.

We propose a flexible anti-metal radio frequency identification (RFID) tag antenna based on a high-conductivity graphene assembly film (HCGAF). The HCGAF has a conductivity of 1.82 × 106 S m-1, a sheet resistance of 25 mΩ and a thickness of 22 µm. The HCGAF is endowed with high conductivity comparable to metal materials and superb flexibility, which is suitable for making antennas for microwave frequencies. Through proper structural design, parameter optimization, semiautomatic manufacturing and experimental measurements, an HCGAF antenna could realize a realized gain of -7.3 dBi and a radiation efficiency of 80%, and the tag could achieve a 6.4 m read range at 915 MHz on a 20 × 20 cm2 flat copper plate. In the meantime, by utilizing flexible polyethylene (PE) foam, good conformality was obtained. The read ranges of the tags attached to curved copper plates with different bending radii were measured, as well as those of those attached to several daily objects. All the results demonstrate the excellent performance of the design, which is highly favorable for practical RFID anti-metal applications.

Compact and Low-Profile UWB Antenna Based on Graphene-Assembled Films for Wearable Applications.

In this article, a graphene-assembled film (GAF)-based compact and low-profile ultra-wide bandwidth (UWB) antenna is presented and tested for wearable applications. The highly conductive GAFs (~106 S/m) together with the flexible ceramic substrate ensure the flexibility and robustness of the antenna, which are two main challenges in designing wearable antennas. Two H-shaped slots are introduced on a coplanar-waveguide (CPW) feeding structure to adjust the current distribution and thus improve the antenna bandwidth. The compact GAF antenna with dimensions of 32 × 52 × 0.28 mm3 provides an impedance bandwidth of 60% (4.3-8.0 GHz) in simulation. The UWB characteristics are further confirmed by on-body measurements and show a bending insensitive bandwidth of ~67% (4.1-8.0 GHz), with the maximum gain at 7.45 GHz being 3.9 dBi and 4.1 dBi in its flat state and bent state, respectively. Our results suggest that the proposed antenna functions properly in close proximity to a human body and can sustain repetitive bending, which make it well suited for applications in wearable devices.

Negative Pressure Pyrolysis Induced Highly Accessible Single Sites Dispersed on 3D Graphene Frameworks for Enhanced Oxygen Reduction.

Herein, we report a negative pressure pyrolysis to access dense single metal sites (Co, Fe, Ni etc.) with high accessibility dispersed on three-dimensional (3D) graphene frameworks (GFs), during which the differential pressure between inside and outside of metal-organic frameworks (MOFs) promotes the cleavage of the derived carbon layers and gradual expansion of mesopores. In situ transmission electron microscopy and Brunauer-Emmett-Teller tests reveal that the formed 3D GFs possess an enhanced mesoporosity and external surface area, which greatly favor the mass transport and utilization of metal sites. This contributes to an excellent oxygen reduction reaction (ORR) activity (half-wave potential of 0.901 V vs. RHE). Theoretical calculations verify that selective carbon cleavage near Co centers can efficiently lower the overall ORR theoretical overpotential in comparison with intact atomic configuration.

Stabilizing Pt Nanocrystals Encapsulated in N-Doped Carbon as Double-Active Sites for Catalyzing Oxygen Reduction Reaction.

Polypropylene fiber, a cheap source of nitrogen-doped carbon, is introduced to design robust nitrogen-doped carbon-encapsulated small Pt nanocrystals with Pt and nitrogen-carbon double-active centers toward oxygen reduction reaction (ORR). Ascribed to the separation effect of the polypropylene fiber, even suffering from a high-temperature carbonization treatment at 720 °C for 90 min, the polypropylene fiber-derived carbon-encapsulated Pt nanocrystal maintains a small particle size (3 nm diameter on average). As expected, its ORR mass activity is up to 116.5 mA/mg at 0.9 V. After 8000 cycles, the half-wave potential of the prepared catalyst declines only by 14 mV compared with 43 mV for the commercial Pt/C catalyst. The significantly improved electrochemical properties of the as-prepared catalyst are resulted from the nitrogen-doped carbon-encapsulated Pt nanocrystal structure, which is benefited to adsorption and activation of oxygen due to the presence of nitrogen-doped carbon as the important active site for ORR besides Pt metal. In addition, the migration, aggregation, and growth of Pt nanoparticles are prohibited in terms of the outer nitrogen-doped carbon protection layer, greatly enhancing the stability of the catalyst.

Ultrahigh Conductive Copper/Large Flake Size Graphene Heterostructure Thin-Film with Remarkable Electromagnetic Interference Shielding Effectiveness.

To guarantee the normal operation of next generation portable electronics and wearable devices, together with avoiding electromagnetic wave pollution, it is urgent to find a material possessing flexibility, ultrahigh conductive, and superb electromagnetic interference shielding effectiveness (EMI SE) simultaneously. In this work, inspired by a building bricks toy with the interlock system, we design and fabricate a copper/large flake size graphene (Cu/LG) composite thin film (≈8.8 µm) in the light of high temperature annealing of a large flake size graphene oxide film followed by magnetron sputtering of copper. The obtained Cu/LG thin-film shows ultrahigh thermal conductivity of over 1932.73 (±63.07) W m-1 K-1 and excellent electrical conductivity of 5.88 (±0.29) × 106 S m-1 . Significantly, it also exhibits a remarkably high EMI SE of over 52 dB at the frequency of 1-18 GHz. The largest EMI SE value of 63.29 dB, accorded at 1 GHz, is enough to obstruct and absorb 99.99995% of incident radiation. To the best of knowledge, this is the highest EMI SE performance reported so far in such thin thickness of graphene-based materials. These outstanding properties make Cu/LG film a promising alternative building block for power electronics, microprocessors, and flexible electronics.

Ultrathin Icosahedral Pt-Enriched Nanocage with Excellent Oxygen Reduction Reaction Activity.

Cost-efficient utilization of Pt in the oxygen reduction reaction (ORR) is of great importance for the potential industrial scale demand of proton-exchange membrane fuel cells. Designing a hollow structure of a Pt catalyst offers a great opportunity to enhance the electrocatalytic performance and maximize the use of precious Pt. Herein we report a routine to synthesize ultrathin icosahedral Pt-enriched nanocages. In detail, the Pt atoms were conformally deposited on the surface of Pd icosahedral seeds, followed by selective removal of the Pd core by a concentrated HNO3 solution. The icosahedral Pt-enriched nanocage that is a few atomic layers thick includes the merits of abundant twin defects, an ultrahigh surface/volume ratio, and an ORR-favored Pt{111} facet, all of which have been demonstrated to be promoting factors for ORR. With a 10 times higher specific activity and 7 times higher mass activity, this catalyst shows more extraordinary ORR activity than the commercial Pt/C. The ORR activity of icosahedral Pt-enriched nanocages outperforms the cubic and octahedral nanocages reported in the literature, demonstrating the superiority of the icosahedral nanocage structure.

Intrinsically Microporous Polymer Retains Porosity in Vacuum Thermolysis to Electroactive Heterocarbon.

Vacuum carbonization of organic precursors usually causes considerable structural damage and collapse of morphological features. However, for a polymer with intrinsic microporosity (PIM-EA-TB with a Brunauer-Emmet-Teller (BET) surface area of 1027 m(2)g(-1)), it is shown here that the rigidity of the molecular backbone is retained even during 500 °C vacuum carbonization, yielding a novel type of microporous heterocarbon (either as powder or as thin film membrane) with properties between those of a conducting polymer and those of a carbon. After carbonization, the scanning electron microscopy (SEM) morphology and the small-angle X-ray scattering (SAXS) Guinier radius remain largely unchanged as does the cumulative pore volume. However, the BET surface area is decreased to 242 m(2)g(-1), but microporosity is considerably increased. The new material is shown to exhibit noticeable electrochemical features including two pH-dependent capacitance domains switching from ca. 33 Fg(-1) (when oxidized) to ca. 147 Fg(-1) (when reduced), a low electron transfer reactivity toward oxygen and hydrogen peroxide, and a four-point-probe resistivity (dry) of approximately 40 MΩ/square for a 1-2 µm thick film.

CoS2/carbon network flexible film with Co-N bond/π-π interaction enables superior mechanical properties and high-rate sodium ion storage.

Flexible electrodes based on conversion-type materials have potential applications in low-cost and high-performance flexible sodium-ion batteries (FSIBs), owing to their high theoretical capacity and appropriate sodiation potential. However, they suffer from flexible electrodes with poor mechanical properties and sluggish reaction kinetics. In this study, freestanding CoS2 nanoparticles coupled with graphene oxides and carbon nanotubes (CoS2/GO/CNTs) flexible films with robust and interconnected architectures were successfully synthesized. CoS2/GO/CNTs flexible film displays high electronic conductivity and superior mechanical properties (average tensile strength of 21.27 MPa and average toughness of 393.18 KJ m-3) owing to the defect bridge for electron transfer and the formation of the π-π interactions between CNTs and GO. In addition, the close contact between the CoS2 nanoparticles and carbon networks enabled by the Co-N chemical bond prevents the self-aggregation of the CoS2 nanoparticles. As a result, the CoS2/GO/CNTs flexible film delivered superior rate capability (213.5 mAh g-1 at 6 A g-1, better than most reported flexible anode) and long-term cycling stability. Moreover, the conversion reaction that occurred in the CoS2/GO/CNTs flexible film exhibited pseudocapacitive behavior. This study provides meaningful insights into the development of flexible electrodes with superior mechanical properties and electrochemical performance for energy storage.

Sharply expanding single-atomically dispersed Fe-N active sites through bidirectional coordination for oxygen reduction.

For Fe-NC systems, high-density Fe-N sites are the basis for high-efficiency oxygen reduction reaction (ORR), and P doping can further lower the reaction energy barrier, especially in the form of metal-P bonding. However, limited to the irregular agglomeration of metal atoms at high temperatures, Fe-P bonds and high-density Fe-N cannot be guaranteed simultaneously. Here, to escape the random and violent agglomeration of Fe species during high-temperature carbonization, triphenylphosphine and 2-methylimidazole with a strong metal coordination capability are introduced together to confine Fe growth. With the aid of such bidirectional coordination, the high-density Fe-N site with Fe-P bonds is realized by in situ phosphorylation of Fe in an Fe-NC system (Fe-P-NC) at high temperatures. Impressively, the content of single-atomically dispersed Fe sites for Fe-P-NC dramatically increases from 2.8% to 65.3% compared with that of pure Fe-NC, greatly improving the ORR activity in acidic and alkaline electrolytes. The theoretical calculation results show that the generated Fe2P can simultaneously facilitate the adsorption of intermediates to Fe-N4 sites and the electron transfer, thereby reducing the reaction energy barrier and obtaining superior ORR activity.

Fast and In-Depth Reconstruction of Two-Dimension Cobalt-Based Zeolitic Imidazolate Framework in Glucose Oxidation Processes.

Currently, metal-organic frameworks (MOFs) have emerged as viable candidates for enduring electrode materials in nonenzyme glucose sensing. However, given the inherent water susceptibility of MOFs and their complete self-reconstruction during the process of electrochemical oxygen evolution in alkaline conditions, we are motivated to explore the truth of MOFs catalyzing glucose oxidation. In this work, we fabricated a two-dimensional cobalt-based zeolitic imidazolate framework (ZIF-L) as the electrode material for catalyzing glucose oxidation in alkaline conditions. Our explorations revealed that while the initial glucose catalytic response varied among ZIF-L samples with differing thicknesses, the ultimate steady-state catalytic performance remained largely consistent. This phenomenon arose from the transformation of ZIF-L with distinct thicknesses into CoOOH with uniform morphological and structural characteristics during the glucose catalysis process. And in situ Raman spectroscopy elucidated the sustained equilibrium within the glucose catalytic system, wherein the dynamic interconversion between CoOOH and Co(OH)2 governs the overall process. This study contributes to an enhanced understanding of the glucose catalytic mechanism aspects of nonenzymatic glucose sensor electrode materials, offering insights that serve as inspiration for the development of advanced glucose electrode materials.

Dual-Circularly Polarized and Flexible Metasurface Antenna Based on Graphene Assembled Film for Satellite Communications.

Traditional metal materials used in electronic devices are often problematic due to issues like bending resistance, oxidation leading to failure, and environmental pollution. To address these challenges, microwave electronic devices are constantly casting around for metal substitute materials with additional characteristics such as flexibility, anticorrosive, and eco-friendly. However, finding suitable materials that are accessible for radiofrequency (RF) applications is a difficult yet promising task. Consequently, a high-performance metasurface antenna based on highly conductive graphene films for satellite communications is developed in this paper. The proposed graphene assembled films (GAFs) have a conductivity of up to 1.13 × 106 S/m. Simulation and measurement results confirm the excellent performance of the designed antenna. Comparative experiments are also conducted on salt spray and mechanical bending between GAF antenna patterns and copper foil counterparts, further demonstrating the outstanding flexible property and corrosion resistance performance of prepared GAFs.

Ambient Electrosynthesis toward Single-Atom Sites for Electrocatalytic Green Hydrogen Cycling.

With the ultimate atomic utilization, well-defined configuration of active sites and unique electronic properties, catalysts with single-atom sites (SASs) exhibit appealing performance for electrocatalytic green hydrogen generation from water splitting and further utilization via hydrogen-oxygen fuel cells, such that a vast majority of synthetic strategies toward SAS-based catalysts (SASCs) are exploited. In particular, room-temperature electrosynthesis under atmospheric pressure offers a novel, safe, and effective route to access SASs. Herein, the recent progress in ambient electrosynthesis toward SASs for electrocatalytic sustainable hydrogen generation and utilization, and future opportunities are discussed. A systematic summary is started on three kinds of ambient electrochemically synthetic routes for SASs, including electrochemical etching (ECE), direct electrodeposition (DED), and electrochemical leaching-redeposition (ELR), associated with advanced characterization techniques. Next, their electrocatalytic applications for hydrogen energy conversion including hydrogen evolution reaction, oxygen evolution reaction, overall water splitting, and oxygen reduction reaction are reviewed. Finally, a brief conclusion and remarks on future challenges regarding further development of ambient electrosynthesis of high-performance and cost-effective SASCs for many other electrocatalytic applications are presented.

Compressed Graphene Assembled Film with Tunable Electrical Conductivity.

Graphene and graphene-based materials gifted with high electrical conductivity are potential alternatives in various related fields. However, the electrical conductivity of the macro-graphene materials is much lower than their metal counterparts. Herein, we improved the electrical conductivity of reduced graphene oxide (rGO) based graphene assembled films (GAFs) by applying a series of compressive stress and systematically investigated the relationship between the compressive stress and the electrical conductivity. The result indicates that with increasing applied compressive stress, the sheet resistance increased as well, while the thickness decreased. Under the combined effect of these two competing factors, the number of charge carriers per unit volume increased dramatically, and the conductivity of compressed GAFs (c-GAFs) showed an initial increasing trend as we applied higher pressure and reached a maximum of 5.37 × 105 S/m at the optimal stress of 450 MPa with a subsequent decrease with stress at 550 MPa. Furthermore, the c-GAFs were fabricated into strain sensors and showed better stability and sensitivity compared with GAF-based sensors. This work revealed the mechanism of the tunable conductivity and presented a facile and universal method for improving the electrical conductivity of macro-graphene materials in a controllable manner and proved the potential applications of such materials in flexible electronics like antennas, sensors, and wearable devices.