It is of great significance to prepare liners with excellent inhibition of energetic plasticizer migration and gas barrier properties. Here, we have successfully prepared magnetic iron oxide decorated reduced-graphene-oxide nanosheets (MRGO) by using ultrasound-assisted method. The obtained MRGO nanosheet-fillers were filled into hydroxyl-terminated polybutadiene (HTPB) which was exposed to a magnetic field (200 mT) to achieve ordered orientation of MRGO in the HTPB matrix (Ordered MRGO/HTPB). The laser confocal microscopy demonstrates that MRGO exhibit ordered orientation structure in HTPB matrix with good dispersion, which renders the HTPB composite liners exhibiting high gas and plasticizer barrier capability, with a reduction of 18.9 % in water vapor permeability and a decrease of 14.1 % in dibutyl phthalate (DBP) migration equilibrium concentration as compared with those of random MRGO embedded HTPB composite liners (Random MRGO/HTPB). Moreover, a theoretical model accounting for such enhanced gas/plasticizer barrier performance of HTPB due to the implantation of order aligned MRGO was established, which shows that the effective diffusion pathways of plasticizer/gas for liner penetration would be significantly enhanced when the MRGO nanosheets are oriented within the HTPB matrix. This work provides an effective and facile strategy toward the design and development of composite liners with high plasticizer/gas barrier performance for industrial applications.
Crystal phase is a key factor determining the properties, and hence functions, of two-dimensional transition-metal dichalcogenides (TMDs)1,2. The TMD materials, explored for diverse applications3-8, commonly serve as templates for constructing nanomaterials3,9 and supported metal catalysts4,6-8. However, how the TMD crystal phase affects the growth of the secondary material is poorly understood, although relevant, particularly for catalyst development. In the case of Pt nanoparticles on two-dimensional MoS2 nanosheets used as electrocatalysts for the hydrogen evolution reaction7, only about two thirds of Pt nanoparticles were epitaxially grown on the MoS2 template composed of the metallic/semimetallic 1T/1T' phase but with thermodynamically stable and poorly conducting 2H phase mixed in. Here we report the production of MoS2 nanosheets with high phase purity and show that the 2H-phase templates facilitate the epitaxial growth of Pt nanoparticles, whereas the 1T' phase supports single-atomically dispersed Pt (s-Pt) atoms with Pt loading up to 10 wt%. We find that the Pt atoms in this s-Pt/1T'-MoS2 system occupy three distinct sites, with density functional theory calculations indicating for Pt atoms located atop of Mo atoms a hydrogen adsorption free energy of close to zero. This probably contributes to efficient electrocatalytic H2 evolution in acidic media, where we measure for s-Pt/1T'-MoS2 a mass activity of 85 ± 23 A [Formula: see text] at the overpotential of -50 mV and a mass-normalized exchange current density of 127 A [Formula: see text] and we see stable performance in an H-type cell and prototype proton exchange membrane electrolyser operated at room temperature. Although phase stability limitations prevent operation at high temperatures, we anticipate that 1T'-TMDs will also be effective supports for other catalysts targeting other important reactions.
S-doping emerged as a promising approach to further improve the catalytic performance of carbon-based materials for organic synthesis. Herein, a facile and gram-scale strategy was developed using zeolitic imidazole frameworks (ZIFs) as a precursor for the fabrication of the ZIF-derived N, S co-doped carbon-supported zinc single-atom catalyst (CNS@Zn1-AA) via the pyrolysis of S-doped ZIF-8, which was modified by aniline, ammonia and thiourea and prepared by one-pot ball milling at room temperature. This catalyst, in which Zn is dispersed as the single atom, displays superior activity in N-alkylation via the hydrogen-borrowing strategy (120 °C, turnover frequency (TOF) up to 8.4 h-1). S-doping significantly enhanced the catalytic activity of CNS@Zn1-AA, as it increased the specific surface area and defects of this material and simultaneously increased the electron density of Zn sites in this catalyst. Furthermore, this catalyst had excellent stability and recyclability, and no obvious loss in activity after eight runs.
Plasmonic photocatalysis for CO2 reduction is attracting increasing attention due to appealing properties and great potential for real applications. In this review, the fundamentals of plasmonic photocatalysis and the most recent developments regarding its application in driving CO2 reduction are reported. Firstly, we present the review on the mechanism of plasmonic photocatalytic CO2 reduction, the energy transfer of plasmon, and the CO2 reduction process on the catalyst surface. Then, the modulation on the plasmonic nanostructures and also the semiconductor counterpart to regulate CO2 photoreduction is discussed. Next, the influence of the core-shell structure and the interface between the plasmonic metal and semiconductor on the CO2 photoreduction performance is also outlined. In addition, the latest progress on the emerging direction regarding the plasmonic photocatalysis for methane dry reforming with CO2 is especially emphasized. Finally, a summary on the challenges and prospects of this promising field are provided.
Controlling the architectures and crystal phases of metal@semiconductor heterostructures is very important for modulating their physicochemical properties and enhancing their application performances. Here, a facile one-pot wet-chemical method to synthesize three types of amorphous SnO2 -encapsulated crystalline Cu heterostructures, i.e., hemicapsule, yolk-shell, and core-shell nanostructures, in which unconventional crystal phases (e.g., 2H, 4H, and 6H) and defects (e.g., stacking faults and twin boundaries) are observed in the crystalline Cu cores, is reported. The hemicapsule Cu@SnO2 heterostructures, with voids that not only expose the Cu core with unconventional phases but also retain the interface between Cu and SnO2 , show an excellent electrocatalytic CO2 reduction reaction (CO2 RR) selectivity toward the production of CO and formate with high Faradaic efficiency (FE) above 90% in a wide potential window from -1.05 to -1.55 V (vs reversible hydrogen electrode (RHE)), and the highest FE of CO2 RR (95.3%) is obtained at -1.45 V (vs RHE). This work opens up a new way for the synthesis of new heterostructured nanomaterials with promising catalytic application.
In this paper, amido-functionalized MOFs with core/shell magnetic particles (Fe3O4@MIL-53(Al)-NH2) was prepared by the solvothermal method and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), Vibrating Sample Magnetometer (VSM) and UV/VIS spectrophotometer. The influence of different factors on the adsorption effect of the pollutant, including adsorbent amounts, adsorption time, ionic strength and pH, were explored. It was found that the amine-decorated Fe3O4@MIL-53(Al)-NH2 were efficient for removal of contaminant, with the adsorption capacity for bisphenol A (234.1 mg/g) and tetracycline (84.8 mg/g) under the optimized conditions. The adsorption kinetics and the equilibrium adsorption data indicated that the adsorption process of BPA and TC was more compatible with the pseudo-second-order kinetic model and the Langmuir model, respectively. The thermodynamic values show the adsorption of the mentioned contaminant was spontaneous and endothermic. Moreover, the Fe3O4@MIL-53(Al)-NH2 adsorbent had good regeneration and reusability capacity after five cyclic utilization. All these results show Fe3O4@MIL-53(Al)-NH2 adsorbent could be a potential candidate for future water purification.
A magnetic metal-organic frameworks adsorbent (Fe3O4@MIL-53(Al)) was prepared by a typical solvothermal method for the removal of bisphenol A (BPA), tetracycline (TC), congo red (CR), and methylene blue (MB). The prepared Fe3O4@MIL-53(Al) composite adsorbent was well characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), X-ray diffraction (XRD), and fourier transform infrared spectrometer (FTIR). The influence of adsorbent quantity, adsorption time, pH and ionic strength on the adsorption of the mentioned pollutants were also studied by a UV/Vis spectrophotometer. The adsorption capacities were found to be 160.9 mg/g for BPA, 47.8 mg/g for TC, 234.4 mg/g for CR, 70.8 mg/g for MB, respectively, which is superior to the other reported adsorbents. The adsorption of BPA, TC, and CR were well-fitted by the Langmuir adsorption isotherm model, while MB followed the Freundlich model, while the adsorption kinetics data of all pollutants followed the pseudo-second-order kinetic models. The thermodynamic values, including the enthalpy change (ΔH°), the Gibbs free energy change (ΔG°), and entropy change (ΔS°), showed that the adsorption processes were spontaneous and exothermic entropy-reduction process for BPA, but spontaneous and endothermic entropy-increasing processes for the others. The Fe3O4@MIL-53(Al) was also found to be easily separated after external magnetic field, can be a potential candidate for future water treatment.
Lattice engineering on specific facets of metal catalysts is critically important not only for the enhancement of their catalytic performance but also for deeply understanding the effect of facet-based lattice engineering on catalytic reactions. Here, we develop a facile two-step method for the lattice expansion on specific facets, i.e., Pt(100) and Pt(111), of Pt catalysts. We first prepare the Pd@Pt core-shell nanoparticles exposed with the Pt(100) and Pt(111) facets, respectively, via the Pd-seeded epitaxial growth, and then convert the Pd core to PdH0.43 by hydrogen intercalation. The lattice expansion of the Pd core induces the lattice enlargement of the Pt shell, which can significantly promote the alcohol oxidation reaction (AOR) on both Pt(100) and Pt(111) facets. Impressively, Pt mass specific activities of 32.51 A mgPt-1 for methanol oxidation and 14.86 A mgPt-1 for ethanol oxidation, which are 41.15 and 25.19 times those of the commercial Pt/C catalyst, respectively, have been achieved on the Pt(111) facet. Density functional theory (DFT) calculations indicate that the remarkably improved catalytic performance on both the Pt(100) and the Pt(111) facets through lattice expansion arises from the enhanced OH adsorption. This work not only paves the way for lattice engineering on specific facets of nanomaterials to enhance their electrocatalytic activity but also offers a promising strategy toward the rational design and preparation of highly efficient catalysts.
Phase engineering of nanomaterials (PEN) enables the preparation of metal nanomaterials with unconventional phases that are different from their thermodynamically stable counterparts. These unconventional-phase nanomaterials can serve as templates to construct precisely controlled metallic heterostructures for wide applications. Nevertheless, how the unconventional phase of templates affects the nucleation and growth of secondary metals still requires systematic explorations. Here, two-dimensional (2D) square-like Au nanosheets with an unconventional 2H/face-centered cubic (fcc) heterophase, composing of two pairs of opposite edges with 2H/fcc heterophase and fcc phase, respectively, and two 2H/fcc heterophase basal planes, are prepared and then used as templates to grow one-dimensional (1D) Rh nanorods. The effect of different phases in different regions of the Au templates on the overgrowth of Rh nanorods has been systematically investigated. By tuning the reaction conditions, three types of 1D/2D Rh-Au heterostructures are prepared. In the type A heterostructure, Rh nanorods only grow on the fcc defects including stacking faults and/or twin boundaries (denoted as fcc-SF/T) and 2H phases in two 2H/fcc edges of the Au nanosheet. In the type B heterostructure, Rh nanorods grow on the fcc-SF/T and 2H phases in two 2H/fcc edges and two 2H/fcc basal planes of the Au nanosheet. In the type C heterostructure, Rh nanorods grow on four edges and two basal planes of the Au nanosheet. Furthermore, the type C heterostructure shows promising performance toward the electrochemical hydrogen evolution reaction (HER) in acidic media, which is among the best reported Rh-based and other noble-metal-based HER electrocatalysts.
Metallic nanostructures are commonly densely packed into a few packing variants with slightly different atomic packing factors. The structural aspects and physicochemical properties related with the vacancies in such nanostructures are rarely explored because of lack of an effective way to control the introduction of vacancy sites. Highly voided metallic nanostructures with ordered vacancies are however energetically high lying and very difficult to synthesize. Here, we report a chemical method for synthesis of hierarchical Rh nanostructures (Rh NSs) composed of ultrathin nanosheets, composed of hexagonal close-packed structure embedded with nanodomains that adopt a vacated Barlow packing with ordered vacancies. The obtained Rh NSs exhibit remarkably enhanced electrocatalytic activity and stability toward the hydrogen evolution reaction (HER) in alkaline media. Theoretical calculations reveal that the exceptional electrocatalytic performance of Rh NSs originates from their unique vacancy structures, which facilitate the adsorption and dissociation of H2O in the HER.
Heterostructured, including heterophase, noble-metal nanomaterials have attracted much interest due to their promising applications in diverse fields. However, great challenges still remain in the rational synthesis of well-defined noble-metal heterophase nanostructures. Herein, we report the preparation of Pd nanoparticles with an unconventional hexagonal close-packed (2H type) phase, referred to as 2H-Pd nanoparticles, via a controlled phase transformation of amorphous Pd nanoparticles. Impressively, by using the 2H-Pd nanoparticles as seeds, Au nanomaterials with different crystal phases epitaxially grow on the specific exposed facets of the 2H-Pd, i.e., face-centered cubic (fcc) Au (fcc-Au) on the (002)h facets of 2H-Pd while 2H-Au on the other exposed facets, to achieve well-defined fcc-2H-fcc heterophase Pd@Au core-shell nanorods. Moreover, through such unique facet-directed crystal-phase-selective epitaxial growth, a series of unconventional fcc-2H-fcc heterophase core-shell nanostructures, including Pd@Ag, Pd@Pt, Pd@PtNi, and Pd@PtCo, have also been prepared. Impressively, the fcc-2H-fcc heterophase Pd@Au nanorods show excellent performance toward the electrochemical carbon dioxide reduction reaction (CO2RR) for production of carbon monoxide with Faradaic efficiencies of over 90% in an exceptionally wide applied potential window from -0.9 to -0.4 V (versus the reversible hydrogen electrode), which is among the best reported CO2RR catalysts in H-type electrochemical cells.
The crystal phase of metal nanocatalysts significantly affects their catalytic performance. Cu-based nanomaterials are unique electrocatalysts for CO2 reduction reaction (CO2RR) to produce high-value hydrocarbons. However, studies to date are limited to the conventional face-centered cubic (fcc) Cu. Here, we report a crystal phase-dependent catalytic behavior of Cu, after the successful synthesis of high-purity 4H Cu and heterophase 4H/fcc Cu using the 4H and 4H/fcc Au as templates, respectively. Remarkably, the obtained unconventional crystal structures of Cu exhibit enhanced overall activity and higher ethylene (C2H4) selectivity in CO2RR compared to the fcc Cu. Density functional theory calculations suggest that the 4H phase and 4H/fcc interface of Cu favor the C2H4 formation pathway compared to the fcc Cu, leading to the crystal phase-dependent C2H4 selectivity. This study demonstrates the importance of crystal phase engineering of metal nanocatalysts for electrocatalytic reactions, offering a new strategy to prepare novel catalysts with unconventional phases for various applications.
We report a general strategy for the fabrication of binder-free, flexible and weavable transition-metal dichalcogenide nanosheet-based hybrid fibers by using well-aligned multi-walled carbon nanotubes as hosts. The resulting hybrid fibers are used as electrodes for electrocatalytic hydrogen evolution, showing excellent performance in both acidic and basic environments, and excellent long-term stability.
Phase engineering of nanomaterials (PEN) offers a promising route to rationally tune the physicochemical properties of nanomaterials and further enhance their performance in various applications. However, it remains a great challenge to construct well-defined crystalline@amorphous core-shell heterostructured nanomaterials with the same chemical components. Herein, the synthesis of binary (Pd-P) crystalline@amorphous heterostructured nanoplates using Cu3- χ P nanoplates as templates, via cation exchange, is reported. The obtained nanoplate possesses a crystalline core and an amorphous shell with the same elemental components, referred to as c-Pd-P@a-Pd-P. Moreover, the obtained c-Pd-P@a-Pd-P nanoplates can serve as templates to be further alloyed with Ni, forming ternary (Pd-Ni-P) crystalline@amorphous heterostructured nanoplates, referred to as c-Pd-Ni-P@a-Pd-Ni-P. The atomic content of Ni in the c-Pd-Ni-P@a-Pd-Ni-P nanoplates can be tuned in the range from 9.47 to 38.61 at%. When used as a catalyst, the c-Pd-Ni-P@a-Pd-Ni-P nanoplates with 9.47 at% Ni exhibit excellent electrocatalytic activity toward ethanol oxidation, showing a high mass current density up to 3.05 A mgPd -1 , which is 4.5 times that of the commercial Pd/C catalyst (0.68 A mgPd -1 ).
Understanding the reaction mechanism for the catalytic process is essential to the rational design and synthesis of highly efficient catalysts. MoS2 has been reported to be an efficient catalyst toward the electrochemical hydrogen evolution reaction (HER), but it still lacks direct experimental evidence to reveal the mechanism for MoS2-catalyzed electrochemical HER process at the atomic level. In this work, we develop a wet-chemical synthetic method to prepare the single-layer MoS2-coated polyhedral Ag core-shell heterostructure (Ag@MoS2) with tunable sizes as efficient catalysts for the electrochemical HER. The Ag@MoS2 core-shell heterostructures are used as ideal platforms for the real-time surface-enhanced Raman spectroscopy (SERS) study owing to the strong electromagnetic field generated in the plasmonic Ag core. The in situ SERS results provide solid Raman spectroscopic evidence proving the S-H bonding formation on the MoS2 surface during the HER process, suggesting that the S atom of MoS2 is the catalytic active site for the electrochemical HER. It paves the way on the design and synthesis of heterostructures for exploring their catalytic mechanism at atomic level based on the in situ SERS measurement.
Various kinds of amorphous materials, such as transition metal dichalcogenides, metal oxides, and metal phosphates, have demonstrated superior electrocatalytic performance compared with their crystalline counterparts. Compared to other materials for electrocatalysis, noble metals exhibit intrinsically high activity and excellent durability. However, it is still very challenging to prepare amorphous noble-metal nanomaterials due to the strong interatomic metallic bonding. Herein, the discovery of a unique thiol molecule is reported, namely bismuthiol I, which can induce the transformation of Pd nanomaterials from face-centered-cubic (fcc) phase into amorphous phase without destroying their integrity. This ligand-induced amorphization is realized by post-synthetic ligand exchange under ambient conditions, and is applicable to fcc Pd nanomaterials with different capping ligands. Importantly, the obtained amorphous Pd nanoparticles exhibit remarkably enhanced activity and excellent stability toward electrocatalytic hydrogen evolution in acidic solution. This work provides a facile and effective method for preparing amorphous Pd nanomaterials, and demonstrates their promising electrocatalytic application.
The fast industrialization process has led to global challenges in the energy crisis and environmental pollution, which might be solved with clean and renewable energy. Highly efficient electrochemical systems for clean-energy collection require high-performance electrocatalysts, including Au, Pt, Pd, Ru, etc. Graphene, a single-layer 2D carbon nanosheet, possesses many intriguing properties, and has attracted tremendous research attention. Specifically, graphene and graphene derivatives have been utilized as templates for the synthesis of various noble-metal nanocomposites, showing excellent performance in electrocatalytic-energy-conversion applications, such as the hydrogen evolution reaction and CO2 reduction. Herein, the recent progress in graphene-based noble-metal nanocomposites is summarized, focusing on their synthetic methods and electrocatalytic applications. Furthermore, some personal insights on the challenges and possible future work in this research field are proposed.
The rational design and synthesis of anisotropic 3D nanostructures with specific composition, morphology, surface structure, and crystal phase is of significant importance for their diverse applications. Here, the synthesis of well-crystalline lotus-thalamus-shaped Pt-Ni anisotropic superstructures (ASs) via a facile one-pot solvothermal method is reported. The Pt-Ni ASs with Pt-rich surface are composed of one Ni-rich "core" with face-centered cubic (fcc) phase, Ni-rich "arms" with hexagonal close-packed phase protruding from the core, and facet-selectively grown Pt-rich "lotus seeds" with fcc phase on the end surfaces of the "arms." Impressively, these unique Pt-Ni ASs exhibit superior electrocatalytic activity and stability toward the hydrogen evolution reaction under alkaline conditions compared to commercial Pt/C and previously reported electrocatalysts. The obtained overpotential is as low as 27.7 mV at current density of 10 mA cm-2 , and the turnover frequency reaches 18.63 H2 s-1 at the overpotential of 50 mV. This work provides a new strategy for the synthesis of highly anisotropic superstructures with a spatial heterogeneity to boost their promising application in catalytic reactions.
Photosynthetic biocatalysts are emerging as a new class of materials, with their sophisticated and intricate structure, which promise improved remarkable quantum efficiency compared to conventional inorganic materials in artificial photosynthesis. To break the limitation of efficiency, the construction of bioconjugated photo-electrochemical conversion devices has garnered substantial interest and stood at the frontier of the multidisciplinary research between biology and chemistry. Herein, a biohybrid photoanode of a photosynthetic membrane protein (Photosystem II (PS II)), extracted from fresh spinach entrapped on mesoporous WO3 film, is fabricated on fluorine-doped tin oxide. The PS II membrane proteins are observed to communicate with the WO3 electrode in the absence of any soluble redox mediators and sacrificial reagents under the visible light of the solar spectrum, even to 700 nm. The biohybrid electrode undergoes electron transfer and generates a significantly enhanced photocurrent compared to previously reported PS II-based photoanodes with carbon nanostructures or other semiconductor substrates for solar water oxidation. The maximum incident photon-to-current conversion efficiency reaches 15.24% at 400 nm in the visible light region. This work provides some insights and possibilities into the efficient assembly of a future solar energy conversion system based on visible-light-responsive semiconductors and photosynthetic proteins.
Light , Membrane Proteins/metabolism , Oxides/chemistry , Photosynthesis , Tungsten/chemistry , Water/chemistry , Electricity , Electrodes , Fluorine/chemistry , Oxidation-Reduction , Photosystem II Protein Complex/metabolism , Porosity , Spinacia oleracea , Tin Compounds/chemistry
Au@ZnO nanospheres with controlled core-shell and yolk-shell features were successfully fabricated through a facile template-based solvothermal method using carbonaceous layers as intermediate. The active carbonaceous layers containing numerous surface functional groups such as OH and CâO play key roles in fabrication of the Au@ZnO nanospheres. The structures of Au@ZnO can easily controlled by adjusting the concentration of Zn ions aqueous solution and/or the size of Au@C microspheres. The synthesis strategy proposed in this paper is also verified to be suitable for fabricating some other Au@metallic oxides nanospheres such as Au@SnO2 and Au@Fe2O3 with controlled structures. Furthermore, due to the synergic effect of the surface plasma resonance effect of Au cores and the large surface area of 122.67 m2 g-1, the Au@ZnO nanospheres with yolk-shell feature exhibite good photocatalytic activity and stability under visible-light irradiation.
