A Self-foaming Strategy to Construct Small Mo2C Nanoparticles Decorated 3D Carbon Foams as Superior Electromagnetic Wave Absorbing Materials with Strong Corrosion Resistance.

3D macroporous carbon-based foams are always considered as promising candidates for high-performance electromagnetic (EM) wave absorbing materials due to the collaborative EM contribution and salutary structure effect. However, the uneven distribution of heterogeneous EM components and the cumbersome preparation process have become key issues to hinder their performance improvement and practical popularity. Herein, the fabrication of 3D carbon foam decorated with small and highly dispersed Mo2C nanoparticles is realized by an innovative self-foaming strategy. The foaming mechanism can be attributed to the decomposition of nitrate during the softening process of organic polymers. The good dispersion of Mo2C nanoparticles boosts interfacial polarization significantly. After regulating the content of Mo2C nanoparticles, the optimal Mo2C/CF-x exhibits good EM absorption performance, whose minimum reflection loss intensity value can reach up to -72.2 dB, and effective absorption bandwidth covers 6.7 GHz with a thickness of 2.30 mm. Very importantly, the resultant Mo2C/CF-x exhibits hydrophobicity and strong acidic anticorrosion, and a long-time treatment in HCl solution (6.0 mol L-1) produces negligible impacts on their EM functions. It is believed that this extraordinary feature may render Mo2C/C foams as qualified and durable EM wave absorbing materials (EWAMs) under rigorous conditions.

Compositional and Hollow Engineering of Silicon Carbide/Carbon Microspheres as High-Performance Microwave Absorbing Materials with Good Environmental Tolerance.

Microwave absorbing materials (MAMs) characterized by high absorption efficiency and good environmental tolerance are highly desirable in practical applications. Both silicon carbide and carbon are considered as stable MAMs under some rigorous conditions, while their composites still fail to produce satisfactory microwave absorption performance regardless of the improvements as compared with the individuals. Herein, we have successfully implemented compositional and structural engineering to fabricate hollow SiC/C microspheres with controllable composition. The simultaneous modulation on dielectric properties and impedance matching can be easily achieved as the change in the composition of these composites. The formation of hollow structure not only favors lightweight feature, but also generates considerable contribution to microwave attenuation capacity. With the synergistic effect of composition and structure, the optimized SiC/C composite exhibits excellent performance, whose the strongest reflection loss intensity and broadest effective absorption reach - 60.8 dB and 5.1 GHz, respectively, and its microwave absorption properties are actually superior to those of most SiC/C composites in previous studies. In addition, the stability tests of microwave absorption capacity after exposure to harsh conditions and Radar Cross Section simulation data demonstrate that hollow SiC/C microspheres from compositional and structural optimization have a bright prospect in practical applications.

Advances in Atomically Dispersed Metal and Nitrogen Co-Doped Carbon Catalysts for Advanced Oxidation Technologies and Water Remediation: From Microenvironment Modulation to Non-Radical Mechanisms.

Atomically dispersed metal and nitrogen co-doped carbon catalysts (M-N-C) have been attracting tremendous attentions thanks to their unique MNx active sites and fantastic catalytic activities in advanced oxidation technologies (AOTs) for water remediation. However, precisely tailoring the microenvironment of active sites at atomic level is still an intricate challenge so far, and understanding of the non-radical mechanisms in persulfate activation exists many uncertainties. In this review, latest developments on the microenvironment modulation strategies of atomically dispersed M-N-C catalysts including regulation of central metal atoms, regulation of coordination numbers, regulation of coordination heteroatoms, and synergy between single-atom catalysts (SACs) with metal species are systematically highlighted and discussed. Afterwards, progress and underlying limitations about the typical non-radical pathways from production of singlet oxygen, electron transfer mechanism to generation of high-valent metal species are well demonstrated to inspire intrinsic insights about the mechanisms of M-N-C/persulfate systems. Lastly, perspectives for the remaining challenges and opportunities about the further development of carbon-based SACs in environment remediation are also pointed out. It is believed that this review will be much valuable for the further design of active sites in M-N-C/persulfate catalytic systems and promote the wide application of SACs in various fields.

State-of-the-art in carbides/carbon composites for electromagnetic wave absorption.

Electromagnetic wave absorbing materials (EWAMs) have made great progress in the past decades, and are playing an increasingly important role in radiation prevention and antiradar detection due to their essential attenuation toward incident EM wave. With the flourish of nanotechnology, the design of high-performance EWAMs is not just dependent on the intrinsic characteristics of single-component medium, but pays more attention to the synergistic effects from different components to generate rich loss mechanisms. Among various candidates, carbides and carbon materials are usually labeled with the features of chemical stability, low density, tunable dielectric property, and diversified morphology/microstructure, and thus the combination of carbides and carbon materials will be a promising way to acquire new EWAMs with good practical application prospects. In this review, we introduce EM loss mechanisms related to dielectric composites, and then highlight the state-of-the-art progress in carbides/carbon composites as high-performance EWAMs, including silicon carbide/carbon, MXene/carbon, molybdenum carbide/carbon, as well as some uncommon carbides/carbon composites and multicomponent composites. The critical information regarding composition optimization, structural engineering, performance reinforcement, and structure-function relationship are discussed in detail. In addition, some challenges and perspectives for the development of carbides/carbon composites are also proposed after comparing the performance of some representative composites.

A "Win-Win" Strategy to Modify Co/C Foam with Carbon Microspheres for Enhanced Dielectric Loss and Microwave Absorption Characteristics.

3D carbon foams have demonstrated their superiority in the field of microwave absorption recently, but the preparation processes of traditional graphene foams are complicated, while some novel carbon foams usually suffer from inadequate dielectric property. Herein, a simple "win-win" strategy is demonstrated to synchronously realize the construction of 3D Co/C foam and its surface decoration with carbon microspheres. Therein, the host Co/C foams and guest carbon microspheres interact with each other, resulting in the improvement of the dispersity of carbon microspheres and Co nanoparticles. The bilaterally synergistic effect can effectively enhance the interfacial polarization and conductive loss of these obtained samples. Electromagnetic analysis reveals that the optimized sample with moderate carbon microsphere content (about 33.5 wt%) displays a widened maximum effective absorption bandwidth of 5.2 GHz and a consolidated reflection loss intensity of -67.6 dB. Besides, the microwave absorption enhancement mechanisms are investigated and discussed in detail. It is believed that this work provides valuable ideas for the development of 3D-foam-based microwave absorbing materials for practical applications.

Surface oxidation protection strategy of CoS2 by V2O5 for electrocatalytic hydrogen evolution reaction.

Transition metal sulfides (TMSs) are promising electrocatalysts for hydrogen evolution reaction (HER), while TMSs usually suffer from inevitable surface oxidation in air, and the impact of the surface oxidation on their HER catalytic activity remains unclear. Herein, we demonstrate an effective strategy for reducing the surface oxidation degree of easily oxidized CoS2 by introducing glued vanadium pentoxide (V2O5) nanoclusters, taking advantage of the preferential adsorption and strong interaction between high-valence V and O2. Combining oxidation protection and elaborate oxidation control experiments reveal that reduced surface oxidation degree of CoS2 is conducive to affording promising HER catalytic performance, as the oxidized surface of CoS2 can hinder the dissociation of water and thus is harmful to the HER process. Direct evidence is provided that surface oxidation should be carefully considered for TMS-based HER catalysts. The present work not only develops a new strategy for protecting CoS2 from surface oxidation, but also provides deep insight into the impact of surface oxidation on the HER performance of transition metal compounds.

Hydroxyl-modified Nb4C3Tx MXene@ZnIn2S4 sandwich structure for photocatalytic overall water splitting.

Herein, a hydroxyl-modified MXene@ZnIn2S4 (Nb4C3Tx MXene@ZIS-OH) overall water splitting photocatalyst with a sandwich structure was prepared through an in-situ growth strategy and peroxyl plasma post-treatment. The Nb4C3Tx MXene@ZIS-OH exhibits outstanding catalytic performance, which generates the release rates of hydrogen (53.8 µmol g-1h-1) and oxygen (26.7 µmol g-1h-1) from the water under visible light irradiation. After four photocatalytic cycling, the photocatalytic overall water splitting activity of Nb4C3Tx MXene@ZIS-OH is still 95.9% of the initial activity, which indicates that Nb4C3Tx MXene@ZIS-OH exhibits excellent cycling stability. Notably, the Nb4C3Tx MXene@ZIS-OH achieves an AQY of 1.2% for the overall photocatalytic water splitting at 380 nm. The sandwich structure and matched heterointerface between high work function Nb4C3Tx MXene and ZnIn2S4 nanosheets promote the electron transport, inhibit the charge recombination, and separate the generated H2 and O2 with effectiveness. Importantly, the Finite-Difference Time-Domain (FDTD) simulation suggests the hydroxyl groups on the surface of ZnIn2S4 could increase the hydrophilicity of photocatalyst and capture the holes generated by photoexcitation, thereby promoting the separation of electron-hole pairs rapidly. This work presents a successful example of constructing overall water splitting photocatalysts by energy level regulation, structure design and functional group modification.

Construction of Ag nanocluster-modified Ag3PO4 containing silver vacancies via in-situ reduction: With enhancing the photocatalytic degradation activity of sulfamethoxazole.

Photocatalytic removal of sulfonamide antibiotics is an effective strategy to solve environmental pollution. Ag3PO4 is a promising anode material for photocatalytic material with photocatalytic degradation ability under ultraviolet light or natural light. Unfortunately, due to its instability, Ag+ could be reduced to Ag0 which loaded onto the surface of Ag3PO4 during the photocatalytic process, causing self-photocorrosion and resulting in the reduction of photocatalytic activity and stability. Herein, Ag3PO4 nanoparticles loaded with Ag nanoclusters containing Ag vacancies (Ag/Ag3PO4-VAg) were constructed by an in-situ reduction strategy to achieve effectively photocatalytic degradation behavior. The Ag nanoclusters loaded on the surface of Ag3PO4 can not only effectively inhibit the self-photocorrosion but also affords a localized surface plasmon resonance (LSPR) effect in the photocatalytic process, thus leading to the efficient generation and rapid transfer of photogenerated carriers behavior. In addition, the Ag vacancies in Ag3PO4 are crucial to increasing the adsorption energy of H2O for further enhancing the capture and accumulation of electrons. In detail, according to Zeta potential analysis, the strong adsorption sites of sulfamethoxazole (SMX) molecules are generated at the interface of Ag and Ag3PO4, which promote the activation of SMX molecules. A 100 ml of 20 mg/L SMX could be completely degraded within 15 min with an apparent rate constant (Kapp) of 0.306 min-1, which far exceeds the activity of most of the photocatalysts. This work may provide an attractive strategy to address the activity, stability of Ag3PO4 and and realizing the green remediation of SMX wastewater.

Unveiling the Coercivity-Induced Electrocatalytic Oxygen Evolution Activity of Single-Domain CoFe2O4 Nanocrystals under a Magnetic Field.

Spin polarization modulation in ferromagnetic materials has become an effective way to promote the electrocatalytic oxygen evolution reaction (OER). Herein, to reveal the coercivity-related OER performance, single-domain ferromagnetic CoFe2O4 (CFO) nanocrystals with different coercivities are synthesized and subjected to OER under an in situ tunable magnetic field. As the more ordered spin polarization state of CFO with a higher coercivity can afford a facilitated electron transfer process, the magnetic field-assisted OER activity can be more improved with an increase in coercivity. Specifically, the decreased magnitudes of the overpotential, Tafel slope, and charge transfer resistance increase on the samples with higher coercivity. The CFO with the largest coercivity (7500 Oe) shows the best OER performance with an overpotential of 350 mV at a current density of 10 mA cm-2 under a magnetic field of 14000 G. In addition, a hysteresis effect that maintains enhanced OER current density after the magnetic field has been withdrawn is observed, where higher coercivity affords a longer hysteresis period. The exploration of coercivity-related OER enhancement may provide new insights into the design and synthesis of promising "magnetic effect" catalysts.

Oxygen Vacancy-Induced Construction of CoO/h-TiO2 Z-Scheme Heterostructures for Enhanced Photocatalytic Hydrogen Evolution.

Environmentally friendly catalysts with excellent performance and low cost are critical for photocatalysis. Herein, using hydrogenated TiO2 (h-TiO2) nanosheets with enriched oxygen vacancies as the support, two-dimensional CoO/h-TiO2 Z-scheme heterostructures are fabricated for hydrogen production through photocatalytic water splitting. It is revealed that the oxygen vacancies in h-TiO2 can inhibit the oxidation of Co2+ into high-valence Co3+ during the hydrothermal reaction and thermal treatment processes. A CoO/h-TiO2 Z-scheme heterostructure possesses a space charge region and a built-in electric field at the interface, and oxygen vacancies in h-TiO2 can provide more reactive sites, which synergistically improve the separation and transportation of photogenerated carriers. As a result, the photocatalytic hydrogen evolution rate achieves 129.75 µmol·h-1 (with 50 mg of photocatalysts) on the optimized CoO/h-TiO2 heterostructures. This work provides a new design idea for the preparation of excellent TiO2-based photocatalysts.

In Situ Growth of Nitrogen-Doped Carbon Nanotubes Based on Hierarchical Ni@C Microspheres for High Efficiency Bisphenol A Removal through Peroxymonosulfate Activation.

N-doped carbon nanotubes (NCNTs) are promising metal-free heterogeneous catalysts toward peroxymonosulfate (PMS) activation in advanced oxidation processes for wastewater remediation. However, conventional CNTs always suffer from serious agglomeration and low N content, which renders their design synthesis as an important topic in the related field. With hierarchical Ni@C microspheres as a nutritious platform, we have successfully induced in situ growth of NCNTs on their surface by feeding melamine under high-temperature inert atmospheres. These as-grown NCNTs with a small diameter (ca. 20 nm) are firmly rooted in Ni@C microspheres and present loose accumulation on their surface, and their relative content can be tailored easily by manipulating the mass ratio of melamine to Ni@C microspheres. The investigation on bisphenol A (BPA) removal reveals that the loading amount of NCNTs affects the catalytic performance greatly, and the optimum ratio of melamine to Ni@C microspheres is 5.0 because the corresponding MNC-5.0 possesses sufficient surface N sites and moderate electron transfer, resulting in powerful PMS activation and sufficient utilization of reactive oxidative species (ROS). MNC-5.0 also addresses its advantages as compared with other NCNTs from post treatment and spontaneous growth strategies. The primary ROS responsible for BPA degradation are identified as hydroxyl radical, sulfate radical, superoxide radical, and singlet oxygen through quenching experiments and electron paramagnetic resonance, and the corresponding catalytic mechanism is also put forward based on these results.

Advances in Carbon-Based Microwave Absorbing Materials.

Electromagnetic (EM) pollution has been evolving as one of the most concerning environmental problems in current society, due to the extensive application of EM technology, from household electronic apparatuses to wireless base stations, as well as military radars [...].

Crystalline-Amorphous Ni2 P4 O12 /NiMoOx Nanoarrays for Alkaline Water Electrolysis: Enhanced Catalytic Activity via In Situ Surface Reconstruction.

Water electrolysis affords a promising approach to large-scale hydrogen yield, but its efficiency is restrained by the sluggish water dissociation kinetics. Here, an efficient bifunctional electrocatalyst of in situ formed crystalline nickel metaphosphate on amorphous NiMoOx nanoarrays supported on nickel foam (c-Ni2 P4 O12 /a-NiMoOx /NF) for both hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline solution is reported. The c-Ni2 P4 O12 /a-NiMoOx /NF can deliver a current density of 10 mA cm-2 at a low potential of 78 mV for HER, and a current density of 20 mA cm-2 at an overpotential of 250 mV for OER. Moreover, it only requires a small cell voltage of 1.55 V at 10 mA cm-2 for robust water splitting with outstanding long-term durability over 84 h. Various spectroscopic studies reveal that in situ surface reconstruction is crucial for the enhanced catalytic activity, where c-Ni2 P4 O12 /a-NiMoOx is transformed into c-Ni2 P4 O12 /a-NiMoO4 during the HER process, and into c-Ni2 P4 O12 /a-NiOOH in the OER process. This work may provide a new strategy for uncovering the catalytic mechanism of crystalline-amorphous catalysts.

Treatment of shale gas produced water by magnetic CuFe2O4/TNTs hybrid heterogeneous catalyzed ozone: Efficiency and mechanisms.

Magnetic spinel ferrite (CuFe2O4) has been applied to catalyze ozone for treating the practical shale gas produced water (PW) in our previous study. In this work, CuFe2O4/titanium nanotubes (TNTs) catalyst was successfully prepared by an impregnation-calcination method. Characterization results revealed that the crystal form of CuFe2O4 was bound to the surface of TNTs, the particle size is much smaller than the pure CuFe2O4 crystal particle, which could weaken the influence of the internal diffusion process on its catalytic efficiency. The experimental results showed that the removal ratio of CODCr in the CuFe2O4/TNTs/O3 system was approximately 14% higher than that of the CuFe2O4/O3 system. The dissolution of metal elements decreased to one-third that of the CuFe2O4/O3 system. The inhibition ratio of PW on the growth of E. coli K12 decreased 68% after the CuFe2O4/TNTs catalytic oxidation process. Experimental results of complete capture experiments illustrated that the yield of HO• of the CuFe2O4/TNTs/O3 system was 10-19% higher than that of the CuFe2O4/O3 system. The elemental valence analysis revealed that the transition of Cu(II)-Cu(III) and Fe(II)-Fe(III) coexisted in the catalytic system. Besides, the surface hydroxyl groups promoted the electron transfer process and enhanced the ozone adsorption affinity. The proposed catalytic mechanisms of the CuFe2O4/TNTs/O3 system were proposed via the above analysis.

Composition Optimization and Microstructure Design in MOFs-Derived Magnetic Carbon-Based Microwave Absorbers: A Review.

Magnetic carbon-based composites are the most attractive candidates for electromagnetic (EM) absorption because they can terminate the propagation of surplus EM waves in space by interacting with both electric and magnetic branches. Metal-organic frameworks (MOFs) have demonstrated their great potential as sacrificing precursors of magnetic metals/carbon composites, because they provide a good platform to achieve high dispersion of magnetic nanoparticles in carbon matrix. Nevertheless, the chemical composition and microstructure of these composites are always highly dependent on their precursors and cannot promise an optimal EM state favorable for EM absorption, which more or less discount the superiority of MOFs-derived strategy. It is hence of great importance to develop some accompanied methods that can regulate EM properties of MOFs-derived magnetic carbon-based composites effectively. This review comprehensively introduces recent advancements on EM absorption enhancement in MOFs-derived magnetic carbon-based composites and some available strategies therein. In addition, some challenges and prospects are also proposed to indicate the pending issues on performance breakthrough and mechanism exploration in the related field.

O, S-Dual-Vacancy Defects Mediated Efficient Charge Separation in ZnIn2S4/Black TiO2 Heterojunction Hollow Spheres for Boosting Photocatalytic Hydrogen Production.

Defective ZnIn2S4 nanosheets/mesoporous black TiO2 heterojunction hollow spheres (H-ZIS/b-TiO2) are prepared through hydrothermal and surface low-temperature hydrogenation strategies, which show broad-spectrum response and excellent charge separation efficiency. This H-ZIS/b-TiO2 flower-like heterojunction hollow spheres with a narrow band gap of ∼1.88 eV expand the light response to visible light and show excellent photocatalytic hydrogen evolution rate (278 µmol h-1 50 mg-1) under visible-light irradiation, which is 1.5 times as high as that of ZnIn2S4/black TiO2 heterojunction hollow spheres (ZIS/b-TiO2) (181 µmol h-1 50 mg-1). The excellent photocatalytic performance is due to the formation of O, S dual vacancies in b-TiO2 and H-ZIS providing more active sites for photocatalytic reaction and improving the charge separation efficiency, heterojunctions promoting transport of photogenerated carriers, and the hollow structure increasing light utilization by reflecting light. The novel heterojunction hollow sphere with high performance has broad application prospects in the field of energy.

Porous cauliflower-like molybdenum disulfide/cadmium sulfide hybrid micro/nano structure: Enhanced visible light absorption ability and photocatalytic activity.

Micro-/nanostructured materials can control the diffraction and propagation of light, thereby providing new optical properties that can be exploited to enhance photocatalytic processes. In this work, a series of the cauliflower-like MoS2/CdS hybrid micro-/nanostructures is synthesized. These structures contain numerous cracks and pores that can enhance the absorption and utilization of light as well as shorten the distance for transferring photogenerated electrons to the catalyst surface. The results of ultraviolet-visible diffuse reflectance absorption spectra show that the composite material has enhanced absorption in the visible light region. Further investigation of the optical characteristics of the synthesized materials using a finite-difference time-domain (FDTD) simulation reveals that the cauliflower-like micro-/nanostructure increases the optical absorption intensity at the MoS2/CdS interface. Notably, the MoS2/CdS hybrid micro-/nanostructures exhibits high photocatalytic hydrogen production activity (9.5 mmol g-1 h-1) and long-lasting cycle stability. This work helps us to further understand the enhancement mechanism of light absorption and utilization by porous structural materials.

Recent Advances in Plasmonic Nanostructures for Enhanced Photocatalysis and Electrocatalysis.

Plasmonic nanomaterials coupled with catalytically active surfaces can provide unique opportunities for various catalysis applications, where surface plasmons produced upon proper light excitation can be adopted to drive and/or facilitate various chemical reactions. A brief introduction to the localized surface plasmon resonance and recent design and fabrication of highly efficient plasmonic nanostructures, including plasmonic metal nanostructures and metal/semiconductor heterostructures is given. Taking advantage of these plasmonic nanostructures, the following highlights summarize recent advances in plasmon-driven photochemical reactions (coupling reactions, O2 dissociation and oxidation reactions, H2 dissociation and hydrogenation reactions, N2 fixation and NH3 decomposition, and CO2 reduction) and plasmon-enhanced electrocatalytic reactions (hydrogen evolution reaction, oxygen reduction reaction, oxygen evolution reaction, alcohol oxidation reaction, and CO2 reduction). Theoretical and experimental approaches for understanding the underlying mechanism of surface plasmon are discussed. A proper discussion and perspective of the remaining challenges and future opportunities for plasmonic nanomaterials and plasmon-related chemistry in the field of energy conversion and storage is given in conclusion.

Heterogeneous Interface Induced the Formation of Hierarchically Hollow Carbon Microcubes against Electromagnetic Pollution.

Carbon materials with multilevel structural features are showing great potentials in electromagnetic (EM) pollution precaution. With ZIF-67 microcubes as a self-sacrificing precursor, hierarchical carbon microcubes with micro/mesoporous shells and hollow cavities have been successfully fabricated with the assistance of rigid SiO2 coating layers. It is found that the SiO2 layer can effectively counteract the inward shrinkage of organic frameworks during high-temperature pyrolysis due to intensive interfacial interaction. The obtained hollow porous carbon microcubes (HPCMCs) exhibit larger Brunauer-Emmett-Teller surface area and pore volume than porous carbon microcubes (PCMCs) directly derived from ZIF-67 microcubes. The unique microstructure is confirmed to be favorable for conductive loss and interfacial polarization, thus boosting the overall dielectric loss capability of carbon materials. Besides, hollow cavity will also promote multiple reflection of incident EM waves and intensify the dissipation of EM energy. As expected, HPCMCs harvest better microwave absorption performance, including strong reflection loss intensity and broad response bandwidth, than many traditional microporous/mesoporous carbon materials. This study provides a new strategy for the construction of hierarchical carbon materials and may inspire the design of carbon-based composites with excellent EM functions.