Mg-MOF-74 Derived Defective Framework for Hydrogen Storage at Above-Ambient Temperature Assisted by Pt Catalyst.

Metal-organic frameworks (MOFs) are promising candidates for room-temperature hydrogen storage materials after modification, thanks to their ability to chemisorb hydrogen. However, the hydrogen adsorption strength of these modified MOFs remains insufficient to meet the capacity and safety requirements of hydrogen storage systems. To address this challenge, a highly defective framework material known as de-MgMOF is prepared by gently annealing Mg-MOF-74. This material retains some of the crystal properties of the original Mg-MOF-74 and exhibits exceptional hydrogen storage capacity at above-ambient temperatures. The MgO5 knots around linker vacancies in de-MgMOF can adsorb a significant amount of dissociated and nondissociated hydrogen, with adsorption enthalpies ranging from -22.7 to -43.6 kJ mol-1, indicating a strong chemisorption interaction. By leveraging a spillover catalyst of Pt, the material achieves a reversible hydrogen storage capacity of 2.55 wt.% at 160 °C and 81 bar. Additionally, this material offers rapid hydrogen uptake/release, stable cycling, and convenient storage capabilities. A comprehensive techno-economic analysis demonstrates that this material outperforms many other hydrogen storage materials at the system level for on-board applications.

Revealing Distance-Dependent Synergy between MnCo2O4 and Co-N-C in Boosting the Oxygen Reduction Reaction.

Synergistic effects have been applied to a variety of hybrid electrocatalysts to improve their activity and selectivity. Understanding the synergistic mechanism is crucial for the rational design of these types of catalysts. Here, we synthesize a MnCo2O4/Co-N-C hybrid electrocatalyst for the oxygen reduction reaction (ORR) and systematically investigate the synergy between MnCo2O4 nanoparticles and Co-N-C support. Theoretical simulations reveal that the synergy is closely related to the distance between active sites. For a pair of remote active sites, the ORR proceeds through the known 2e- + 2e- relay catalysis while the direct 4e- ORR occurs on a pair of adjacent active sites. Therefore, the formation of the undesired byproduct (H2O2) is inhibited at the interface region between MnCo2O4 and Co-N-C. This synergistic effect is further verified on an anion-exchange membrane fuel cell. The findings deepen the understanding of synergistic catalysis and will provide guidance for the rational design of hybrid electrocatalysts.

Single-crystal ZrCo nanoparticle for advanced hydrogen and H-isotope storage.

Hydrogen-isotope storage materials are essential for the controlled nuclear fusion. However, the currently used smelting-ZrCo alloy suffers from rapid degradation of performance due to severe disproportionation. Here, we reveal a defect-derived disproportionation mechanism and report a nano-single-crystal strategy to solve ZrCo's problems. Single-crystal nano-ZrCo is synthesized by a wet-chemistry method and exhibits excellent comprehensive hydrogen-isotope storage performances, including ultrafast uptake/release kinetics, high anti-disproportionation ability, and stable cycling, far superior to conventional smelting-ZrCo. Especially, a further incorporation of Ti into nano-ZrCo can almost suppress the disproportionation reaction. Moreover, a mathematical relationship between dehydrogenation temperature and ZrCo particle size is established. Additionally, a microwave method capable of nondestructively detecting the hydrogen storage state of ZrCo is developed. The proposed disproportionation mechanism and anti-disproportionation strategy will be instructive for other materials with similar problems.

Homogeneous-heterogeneous interfaces in 2D/2D CoAl/Co9S8/Ni3S4 heterostructures for electromagnetic wave absorption.

Exploring electromagnetic wave (EMW) absorbers with ultrathin matching thickness (d ≤ 1.5 mm), strong reflection loss (RL ≤ -50 dB), and wide effective absorption bandwidth (EAB, RL ≤ -10 dB) is urgent and essential for reducing EMW radiation and interference. Herein, a 2D/2D CoAl/Co9S8/Ni3S4 heterostructure was constructured using simple hydrothermal and pyrolysis methods. 2D porous CoAl nanosheets and 2D Co9S8/Ni3S4 ultrathin nanosheets are assembled by small nanoparticle chains. Strikingly, the CoAl/Co9S8/Ni3S4 heterostructure exhibits remarkable EMW absorption performance with a RL value of -61.56 dB, a high EAB of 4 GHz, and an ultrathin matching thickness of 1.25 mm. Mechanism investigations reveal that the CoAl/Co9S8/Ni3S4 heterostructure delivers dual metal sulfides behavior, high specific surface area, strong interactions, rich defects (N doping), and abundant homogeneous and heterogeneous interfaces, which promote good impedance matching, dielectric loss (interface polarization, conductive loss, and dipole polarization), as well as magnetic loss (natural resonance, exchange resonance, and eddy current loss) characteristics. This work can provide insights into the mechanism of dual metal sulfides used as high-performance EMW absorbers and deepen our understanding of the design and application of 2D/2D heterostructures.

Functional Tailoring of Multi-Dimensional Pure MXene Nanostructures for Significantly Accelerated Electromagnetic Wave Absorption.

Transition metal carbide (Ti3 C2 Tx MXene), with a large specific surface area and abundant surface functional groups, is a promising candidate in the family of electromagnetic wave (EMW) absorption. However, the high conductivity of MXene limits its EMW absorption ability, so it remains a challenge to obtain outstanding EMW attenuation ability in pure MXene. Herein, by integrating HF etching, KOH shearing, and high-temperature molten salt strategies, layered MXene (L-MXene), network-like MXene nanoribbons (N-MXene NRs), porous MXene monolayer (P-MXene ML), and porous MXene layer (P-MXene L) are rationally constructed with favorable microstructures and surface states for EMW absorption. HF, KOH, and KCl/LiCl are used to functionalize MXene to tune its microstructure and surface state (F- , OH- , and Cl- terminals), thereby improving the EMW absorption capacity of MXene-based nanostructures. Impressively, with the unique structure, proper electrical conductivity, large specific surface area, and abundant porous defects, MXene-based nanostructures achieve good impedance matching, dipole polarization, and conduction loss, thus inheriting excellent EMW absorption performance. Consequently, L-MXene, N-MXene NRs, P-MXene ML, and P-MXene L enable a reflection loss (RL ) value of -43.14, -63.01, -60.45, and -56.50 dB with a matching thickness of 0.95, 1.51, 3.83, and 4.65 mm, respectively.

Phase Transformation and Performance of Mg-Based Hydrogen Storage Material by Adding ZnO Nanoparticles.

ZnO nanoparticles in a spherical-like structure were synthesized via filtration and calcination methods, and different amounts of ZnO nanoparticles were added to MgH2 via ball milling. The SEM images revealed that the size of the composites was about 2 µm. The composites of different states were composed of large particles with small particles covering them. After the absorption and desorption cycle, the phase of composites changed. The MgH2-2.5 wt% ZnO composite reveals excellent performance among the three samples. The results show that the MgH2-2.5 wt% ZnO sample can swiftly absorb 3.77 wt% H2 in 20 min at 523 K and even at 473 K for 1 h can absorb 1.91 wt% H2. Meanwhile, the sample of MgH2-2.5 wt% ZnO can release 5.05 wt% H2 at 573 K within 30 min. Furthermore, the activation energies (Ea) of hydrogen absorption and desorption of the MgH2-2.5 wt% ZnO composite are 72.00 and 107.58 KJ/mol H2, respectively. This work reveals that the phase changes and the catalytic action of MgH2 in the cycle after the addition of ZnO, and the facile synthesis of the ZnO can provide direction for the better synthesis of catalyst materials.

Thermal stability of Ni3ZnC0.7: As tunable additive for biomass-derived carbon sheet composites with efficient microwave absorption.

With the rapidly development of radar detection technology and the increasingly complex application environment in military field and electromagnetic pollution surrounded by electron devices, increasingly demand is needed for electromagnetic wave absorbent materials with high absorption efficiency and thermal stability. Herein, a novel Ni3ZnC0.7/Ni loaded puffed-rice derived carbon (RNZC) composites are successfully prepared by vacuum filtration of metal-organic frameworks gel precursor together with layered porous-structure carbon and followed by calcination. The Ni3ZnC0.7 particles uniformly decorate on the surface and pores of puffed-rice derived carbon. The puffed-rice derived carbon@Ni3ZnC0.7/Ni-400 mg (RNZC-4) sample displayed the best electromagnetic wave absorption (EMA) performances among the samples with different Ni3ZnC0.7 loading. The minimum reflection loss (RLmin) of the RNZC-4 composite reaches -39.9 dB at 8.6 GHz, while widest effective absorption bandwidth (EAB) of RNZC-4 for RL < -10 dB can reach 9.9 GHz (8.1-18 GHz, 1.49 mm). High porosity and large specific surface area promote the multiple reflection-absorption effect of the incident electromagnetic waves. The Ni3ZnC0.7 nanoparticles provide a large number of interfaces and dipole factors. Analysis reveals that the RNZC-4 remained general stability under 400 °C with formation of a small amount of NiO and ZnO phases. Surprisingly, at such high temperature, the absorbing properties of the material are improved rather than decreased. Obviously, the material still maintains good electromagnetic wave performance at high temperature, and implies that the absorber shows good performance stability. Therefore, our preparations exhibit potential applications under extreme conditions and a new insight for the design and application of bimetallic carbides.

Honeycomb ZrCo Intermetallic for High Performance Hydrogen and Hydrogen Isotope Storage.

Hydrogen isotope storage materials are of great significance for controlled nuclear fusion, which is promising to provide unlimited clean and dense energy. Conventional storage materials of micrometer-sized polycrystalline ZrCo alloys prepared by the smelting method suffer from slow kinetics, pulverization, disproportionation, and poor cycling stability. Here, we synthesize a honeycomb-structured ZrCo composed of highly crystalline submicrometer ZrCo units using electrospray deposition and magnesiothermic reduction. Compared with conventional ones, honeycomb ZrCo does not require activation and exhibits more than 1 order of magnitude increase in kinetic property. Owing to low defects and low stress, the anti-disproportionation ability and cycling stability of honeycomb ZrCo are also obviously higher than those of conventional ZrCo. Moreover, the interfacial stress (due to hydrogenation/dehydrogenation) as a function of particle radius is established, quantitatively elucidating that small-sized ZrCo reduces stress and pulverization. This study points out a direction for the structural design of ZrCo alloy with high-performance hydrogen isotope storage.

Ultrathin Nanotube Structure for Mass-Efficient and Durable Oxygen Reduction Reaction Catalysts in PEM Fuel Cells.

It remains a challenge for platinum-based oxygen reduction reaction catalysts to simultaneously possess high mass activity and high durability in proton-exchange-membrane fuel cells. Herein, we report ultrathin holey nanotube (UHT)-structured Pt-M (M = Ni, Co) alloy catalysts that achieve unprecedented comprehensive performance. The nanotubes have ultrathin walls of 2-3 nm and construct self-supporting network-like catalyst layers with thicknesses of less than 1 µm, which have efficient mass transfer and 100% surface exposure, thus enabling high utilization of Pt atoms. Combined with the high intrinsic activity produced by the alloying effect, the catalysts achieve high mass activity. Moreover, the nanotube structure not only avoids the agglomeration problem of nanoparticles, but the low curvature of the tube wall also gives UHT a low surface energy (less than 1/3 of that of the same size nanoparticle), so UHT is more resistant to the Ostwald ripening and is stable. For the first time, the U.S. DOE mass activity target and dual durability targets for load and start-stop cycles are achieved on one catalyst. This study provides an effective structural strategy for the preparation of electrocatalysts with high atomic efficiency and excellent durability.

MXene-Reinforced Liquid Metal/Polymer Fibers via Interface Engineering for Wearable Multifunctional Textiles.

Stretchable conductive fibers are an important component of wearable electronic textiles, but often suffer from a decrease in conductivity upon stretching. The use of liquid metal (LM) droplets as conductive fillers in elastic fibers is a promising solution. However, there is an urgent need to develop effective strategies to achieve high adhesion of LM droplets to substrates and establish efficient electron transport paths between droplets. Here, we use large-sized MXene two-dimensional conductive materials to modify magnetic LM droplets and prepare MXene/magnetic LM/poly(styrene-butadiene-styrene) composite fibers (MLMS fibers). The MXene sheets decorated on the surface of magnetic LM droplets not only enhance the droplet adhesion to substrate but also bridge adjacent droplets to establish efficient conductive paths. MLMS fibers show several-fold improvements in tensile strength and elongation and a 30-fold increase in conductivity compared with pure LM-filled fibers. These conductive fibers can be easily woven into multifunctional textiles, which exhibit strong electromagnetic interference shielding and stable Joule heating performances even under large tensile deformation. In addition, other advantages of MLMS textiles, such as high gas/liquid permeability, strong chemical resistance (acid and alkaline conditions), high/low-temperature tolerance (-40-150 °C) and water washability, make them particularly suitable for wearable applications.

Coupling between the 2D "Ligand" and 2D "Host" and Their Assembled Hierarchical Heterostructures for Electromagnetic Wave Absorption.

Constructing the strong interaction between the matrix and the active centers dominates the design of high-performance electromagnetic wave (EMW) absorption materials. However, the interaction-relevant absorption mechanism is still unclear, and the design of ultrahigh reflection loss (RL < -80 dB) absorbers remains a great challenge. Herein, CoFe-based Prussian blue (PB) nanocubes are coprecipitated on the surface of ultrathin CoAl-LDH nanoplates with the assistance of unsaturated coordination sites. During the subsequent pyrolysis process, CoAl-LDH serves as a "ligand" providing a Co source and reacts with Fe or C in the CoFe-PB "host" to form stable CoFe alloys or CoCx species. As a result, strong reactions emerged between the CoAl-LDH matrix and the active CoFe-CoCx@NC centers. Based on the experimental results, the CoAl/CoFe-CoCx@NC hierarchical heterostructure delivers good dielectric losses (dipolar polarization, interface polarization, and conductive loss), magnetic losses (eddy current loss, natural resonance, and exchange resonance), and impedance matching, resulting in a remarkable EMW absorption performance with a reflection loss (RL) value of -82.1 dB at a matching thickness of 3.8 mm. Theoretical results (commercial CST) identify that the strong interaction between the 2D CoAl-LDH "ligand" and 2D CoFe-CoCx "host" promotes a robust heterointerface among the nanoparticles, nanosheets, and nanoplates, which extremely contribute to the dielectric loss. Meanwhile, the coupling effect of nanosheets and nanoplates greatly contributes to the matching performance. This work provides an aggressive strategy for the effect of ligands and hosts on high-performance EMW absorption.

Iron atom-cluster interactions increase activity and improve durability in Fe-N-C fuel cells.

Simultaneously increasing the activity and stability of the single-atom active sites of M-N-C catalysts is critical but remains a great challenge. Here, we report an Fe-N-C catalyst with nitrogen-coordinated iron clusters and closely surrounding Fe-N4 active sites for oxygen reduction reaction in acidic fuel cells. A strong electronic interaction is built between iron clusters and satellite Fe-N4 due to unblocked electron transfer pathways and very short interacting distances. The iron clusters optimize the adsorption strength of oxygen reduction intermediates on Fe-N4 and also shorten the bond amplitude of Fe-N4 with incoherent vibrations. As a result, both the activity and stability of Fe-N4 sites are increased by about 60% in terms of turnover frequency and demetalation resistance. This work shows the great potential of strong electronic interactions between multiphase metal species for improvements of single-atom catalysts.

Environmentally Tough and Stretchable MXene Organohydrogel with Exceptionally Enhanced Electromagnetic Interference Shielding Performances.

Conductive hydrogels have potential applications in shielding electromagnetic (EM) radiation interference in deformable and wearable electronic devices, but usually suffer from poor environmental stability and stretching-induced shielding performance degradation. Although organohydrogels can improve the environmental stability of materials, their development is at the expense of reducing electrical conductivity and thus weakening EM interference shielding ability. Here, a MXene organohydrogel is prepared which is composed of MXene network for electron conduction, binary solvent channels for ion conduction, and abundant solvent-polymer-MXene interfaces for EM wave scattering. This organohydrogel possesses excellent anti-drying ability, low-temperature tolerance, stretchability, shape adaptability, adhesion and rapid self-healing ability. Two effective strategies have been proposed to solve the problems of current organohydrogel shielding materials. By reasonably controlling the MXene content and the glycerol-water ratio in the gel, MXene organohydrogel can exhibit exceptionally enhanced EM interference shielding performances compared to MXene hydrogel due to the increased physical cross-linking density of the gel. Moreover, MXene organohydrogel shows attractive stretching-enhanced interference effectiveness, caused by the connection and parallel arrangement of MXene nanosheets. This well-designed MXene organohydrogel has potential applications in shielding EM interference in deformable and wearable electronic devices.

Facile Synthesis of Amorphous MoCo Lamellar Hydroxide for Alkaline Water Oxidation.

To find an oxygen evolution reaction (OER) catalyst with satisfactory catalytic performance and affordable cost is of great importance to the development of many new energy devices. In this work, a simple and effective strategy was developed to synthesize a series of amorphous MoCo lamellar hydroxide through one-step chemical co-precipitation. Systematic investigations showed that different functional agents (2-methylimidazole, NaOH, NH4 OH) in the fabrication process resulted in different micromorphology of the catalyst, thus influencing its electrocatalytic performance. Also, adding various amounts of Mo could influence the intrinsic catalytic properties. Samples synthesized with appropriate functional agent addition and optimized Mo addition exhibited amorphous nature and bent nanosheet morphology, as well as highest intrinsic catalytic activity, showing a low overpotential of 290 mV at 10 mA cm-2 and a small Tafel slope of 55 mV dec-1 in 1 m KOH solution. Additionally, the catalytic performance of the sample showed just small decay after 50 h chronopotentiometry test and 3000 cyclic voltammetry cycles, exhibiting the ultra-stable catalytic activity of the catalyst. This work provides a possible large-scale commercial production strategy of OER catalysts with promising performance and low fabrication cost.

Hydrogen Passivation of M-N-C (M = Fe, Co) Catalysts for Storage Stability and ORR Activity Improvements.

M-N-C (M = Fe, Co) are highly active nonprecious metal electrocatalysts for the oxygen reduction reaction (ORR) and other applications. Although their operation stability has been extensively studied in proton-exchange-membrane fuel cells, the storage stability that determines the performance maintenance before use has not yet been understood. Here, it is found that long-term exposure of M-N-C catalysts in air would cause surface oxidation and hydroxylation, resulting in significant decrease of ORR activity and fuel-cell performances. Hydrogen passivation is demonstrated to be an effective strategy to protect the atomic M-N4 active sites and improve the storage stability of the catalysts. In addition, the hydrogen-termination can also reduce the ORR energy barrier and increase the utilization of active sites, leading to the improvements of fuel-cell activity and power density. Notably, these findings help to understand the storage-associated degradation and protection of M-N-C catalysts.

Multiple reflection and scattering effects of the lotus seedpod-based activated carbon decorated with Co3O4 microwave absorbent.

The lotus seedpod-based activated carbon (LSAC) is derived from pyrolysis of lotus seedpod as biomass carbon precursor, and Co3O4 is then deposited to LSAC by oxidation-precipitation and crystallization process of Co ions from Co(NO3)2 solution. The Co3O4 particles uniformly decorate on the surface and/or the inner channels of LSAC. The optimal reflection loss (RL) value of LSAC/Co3O4-paraffin wax (PW) composite reaches -39.8 dB, and the bandwidth for RL below -10 dB and -20 dB are 10.3 and 3.0 GHz, respectively, much better than that of LSAC-PW composite for the higher magnetic loss. The addition of Co3O4 particles in LSAC-PW composite significantly enhance the RL values in various thicknesses. The channels of the LSAC and decorated Co3O4 can improve the abilities of multiple scattering, dipole polarization, interface polarization and magnetic loss. This composite provides a promising method to construct high performance absorbers by using biomass carbon to tune the dielectric properties of the ferromagnetic materials.

Efficient microwave absorber and supercapacitors derived from puffed-rice-based biomass carbon: Effects of activating temperature.

Biomass-based carbon is gaining increasing attention because it presents a promising prospect for economic growth and social sustainable development. Moreover, it is an excellent medium for application in electromagnetic and electronic devices. Here, puffed-rice-based carbon is obtained at various activating temperatures, and when the hollow bulges on the carbon disappear, the morphology of the carbon changes into sheet-like structures. The R-800 sample displays the highest ID/IG value and demonstrates the best performance when used as both a microwave absorber and an electrode material. The minimum reflection loss (RL) and bandwidth for RL < -10 dB of the R-800 sample reach -72.1 dB and 13.2 GHz, respectively, and the bandwidth for RL < -20 dB is as large as 7.0 GHz, illustrating the widest bandwidth among the five carbon specimens. The multiple reflection effects and scattering, good impedance matching, and interfacial polarization synergistically enhance the microwave absorption performances of the sample. At 1 A g-1, the specific capacitance of the R-800 sample reaches 117.2 F g-1 and the capacitance retention remains at 85.3%. Moreover, a hybrid supercapacitor R-800//R-800 demonstrates an outstanding energy density of 15.23 Wh kg-1, power density of 5739.43 W kg-1, and high cycle stability (94.5% after 5000 cycles). This functionalized biomass carbon provides a promising media for constructing a bridge between sustainable development and biomass materials.

Hydrogen storage in incompletely etched multilayer Ti2CTx at room temperature.

Hydrogen storage materials are the key to hydrogen energy utilization. However, current materials can hardly meet the storage capacity and/or operability requirements of practical applications. Here we report an advancement in hydrogen storage performance and related mechanism based on a hydrofluoric acid incompletely etched MXene, namely, a multilayered Ti2CTx (T is a functional group) stack that shows an unprecedented hydrogen uptake of 8.8 wt% at room temperature and 60 bar H2. Even under completely ambient conditions (25 °C, 1 bar air), Ti2CTx is still able to retain ~4 wt% hydrogen. The hydrogen storage is stable and reversible in the material, and the hydrogen release is controllable by pressure and temperature below 95 °C. The storage mechanism is deduced to be a nanopump-effect-assisted weak chemisorption in the sub-nanoscale interlayer space of the material. Such a storage approach provides a promising strategy for designing practical hydrogen storage materials.

Carbon Fibers Embedded with Aligned Magnetic Particles for Efficient Electromagnetic Energy Absorption and Conversion.

Harvesting electromagnetic (EM) energy from the environment and converting it into useful micropower is a new and ideal way to eliminate EM radiation and while providing power for microelectronic devices. The key material of this technology is broadband, ultralight, and ultrathin EM-wave-absorbing materials, whose preparation remains challenging. Herein, a high magnetic field (HMF) strategy is proposed to prepare a biomass-derived CoFe/carbon fiber (CoFe/CF) composite, in which CoFe magnetic particles are aligned in CFs, creating magnetic coupling and fast electron transmission channels. The graphitization degree of CFs is improved via the "migration catalysis" of CoFe particles under HMF. The HMF-derived CoFe/CF shows a largely broadened EM wave absorption bandwidth under ultralight and ultrathin conditions (1.5 mm). Its absorption bandwidth increases 5-10 times compared with conventional CoFe/CF that has randomly distributed CoFe particles and surpasses the reported analogues. A device model for EM energy absorption and reuse is designed based on the HMF-derived CoFe/CF membrane, which exhibits a 300% higher capability than conventional CoFe/CF membrane in converting EM energy to thermal energy. This work offers a new strategy for the design and fabrication of broadband, ultrathin, and ultralight EM wave absorption materials and demonstrates a potential conversion approach of the waste EM energy.

Hierarchical Cobalt Selenides as Highly Efficient Microwave Absorbers with Tunable Frequency Response.

Microwave absorbing materials have attracted much attention in solving electromagnetic interference and pollution problems. Hierarchical cobalt selenides have been obtained through a facile selenization annealing process. The as-prepared samples exhibit distinct reflection losses (RL) and frequency responses via tailoring their crystalline configurations, with excellent absorption in Ku, X, or C band. All of the samples show RL greater than or near -50 dB with effective bandwidths more than 4 GHz, indicating that they may serve as high-efficient and frequency-tunable microwave absorbers. Especially, the sample annealed at 400 °C shows a competitive RL of -62.04 dB at 9.92 GHz with a thickness of 2.25 mm; meanwhile, its effective absorption bandwidth reaches 5.36 GHz with a thickness as small as 1.56 mm. The cobalt selenides as microwave absorbers exhibit a promising prospect applied in complex electromagnetic environments.