Phase-dependent growth of Pt on MoS2 for highly efficient H2 evolution.

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.

Plasmonic Photocatalysis for CO2 Reduction: Advances, Understanding and Possibilities.

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.

Selective Epitaxial Growth of Rh Nanorods on 2H/fcc Heterophase Au Nanosheets to Form 1D/2D Rh-Au Heterostructures for Highly Efficient Hydrogen Evolution.

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.

Hydrogen-Intercalation-Induced Lattice Expansion of Pd@Pt Core-Shell Nanoparticles for Highly Efficient Electrocatalytic Alcohol Oxidation.

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.

Ethylene Selectivity in Electrocatalytic CO2 Reduction on Cu Nanomaterials: A Crystal Phase-Dependent Study.

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.

Phase-Selective Epitaxial Growth of Heterophase Nanostructures on Unconventional 2H-Pd Nanoparticles.

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.

Ag@MoS2 Core-Shell Heterostructure as SERS Platform to Reveal the Hydrogen Evolution Active Sites of Single-Layer MoS2.

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.

Interfacing Photosynthetic Membrane Protein with Mesoporous WO3 Photoelectrode for Solar Water Oxidation.

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.

Controlled Synthesis and Photocatalytic Performance of Au@ZnO Nanospheres with Core-Shell and Yolk-Shell Structures Assisted by Carbonaceous Layers as Intermediate.

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 C═O 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.

Elemental Boron for Efficient Carbon Dioxide Reduction under Light Irradiation.

The photoreduction of CO2 is attractive for the production of renewable fuels and the mitigation of global warming. Herein, we report an efficient method for CO2 reduction over elemental boron catalysts in the presence of only water and light irradiation through a photothermocatalytic process. Owing to its high solar-light absorption and effective photothermal conversion, the illuminated boron catalyst experiences remarkable self-heating. This process favors CO2 activation and also induces localized boron hydrolysis to in situ produce H2 as an active proton source and electron donor for CO2 reduction as well as boron oxides as promoters of CO2 adsorption. These synergistic effects, in combination with the unique catalytic properties of boron, are proposed to account for the efficiency of the CO2 reduction. This study highlights the promise of photothermocatalytic strategies for CO2 conversion and also opens new avenues towards the development of related solar-energy utilization schemes.

Promoting Active Species Generation by Plasmon-Induced Hot-Electron Excitation for Efficient Electrocatalytic Oxygen Evolution.

Water splitting represents a promising technology for renewable energy conversion and storage, but it is greatly hindered by the kinetically sluggish oxygen evolution reaction (OER). Here, using Au-nanoparticle-decorated Ni(OH)2 nanosheets [Ni(OH)2-Au] as catalysts, we demonstrate that the photon-induced surface plasmon resonance (SPR) excitation on Au nanoparticles could significantly activate the OER catalysis, specifically achieving a more than 4-fold enhanced activity and meanwhile affording a markedly decreased overpotential of 270 mV at the current density of 10 mA cm(-2) and a small Tafel slope of 35 mV dec(-1) (no iR-correction), which is much better than those of the benchmark IrO2 and RuO2, as well as most Ni-based OER catalysts reported to date. The synergy of the enhanced generation of Ni(III/IV) active species and the improved charge transfer, both induced by hot-electron excitation on Au nanoparticles, is proposed to account for such a markedly increased activity. The SPR-enhanced OER catalysis could also be observed over cobalt oxide (CoO)-Au and iron oxy-hydroxide (FeOOH)-Au catalysts, suggesting the generality of this strategy. These findings highlight the possibility of activating OER catalysis by plasmonic excitation and could open new avenues toward the design of more-energy-efficient catalytic water oxidation systems with the assistance of light energy.

Improved Photocatalytic H2 Evolution over G-Carbon Nitride with Enhanced In-Plane Ordering.

A series of rod-like porous graphitic-carbon nitrides (short as CNs) with enhanced in-plane ordering have been fabricated through self-assembled heptazine hydrate precursors for the first time. By controlling the calcination of the preformed precursors with different temperature-rising rates, the resulted CNs (SAHEP-CNs-1) with the most ordered and least stacked graphitic planar are showing a tremendously improved hydrogen evolution rate of 420 µmol h-1 under visible light and a remarkable apparent quantum efficiency of 8.9% at 420 nm, which is among the highest values for C3 N4 -related photocatalysts in the literature. This work discloses that enhancing in-plane ordering is one critical factor for improving the photocatalytic H2 evolution of carbon nitride, which is an effective solution to prolong the lifetime of charge carriers by accelerating the charge transport and separation within the graphitic planar. This finding would present a facial strategy for the designing of efficient organic semiconductors for photocatalysis.

Efficient visible driven photocatalyst, silver phosphate: performance, understanding and perspective.

Photocatalysis is a promising technology that can contribute to renewable energy production from water and water purification. In order to further develop the field and meet industrial requirements, it is imperative to focus on advancing high efficiency visible light photocatalysts, such as silver phosphate (Ag3PO4). This review aims to highlight the recent progress made in the field, focusing on oxygen production from water, and organic contaminant decomposition using Ag3PO4. The most important advances are discussed and explained in detail, including semiconductor-semiconductor junctions, metal-semiconductor junctions, exposing facet control, and fundamental understanding using advanced spectroscopies and computational chemistry. The review then concludes by critically summarising both findings and current perspectives, and ultimately how the field might best advance in the near future.

Efficient Visible-Light-Driven Carbon Dioxide Reduction by a Single-Atom Implanted Metal-Organic Framework.

Modular optimization of metal-organic frameworks (MOFs) was realized by incorporation of coordinatively unsaturated single atoms in a MOF matrix. The newly developed MOF can selectively capture and photoreduce CO2 with high efficiency under visible-light irradiation. Mechanistic investigation reveals that the presence of single Co atoms in the MOF can greatly boost the electron-hole separation efficiency in porphyrin units. Directional migration of photogenerated excitons from porphyrin to catalytic Co centers was witnessed, thereby achieving supply of long-lived electrons for the reduction of CO2 molecules adsorbed on Co centers. As a direct result, porphyrin MOF comprising atomically dispersed catalytic centers exhibits significantly enhanced photocatalytic conversion of CO2 , which is equivalent to a 3.13-fold improvement in CO evolution rate (200.6 µmol g-1 h-1 ) and a 5.93-fold enhancement in CH4 generation rate (36.67 µmol g-1 h-1 ) compared to the parent MOF.

Nature-Inspired Environmental "Phosphorylation" Boosts Photocatalytic H2 Production over Carbon Nitride Nanosheets under Visible-Light Irradiation.

Inspired by the crucial roles of phosphates in natural photosynthesis, we explored an environmental "phosphorylation" strategy for boosting photocatalytic H2 production over g-C3N4 nanosheets under visible light. As expected, a substantial improvement was observed in the rate of H2 evolution to 947 µmol h(-1), and the apparent quantum yield was as high as 26.1% at 420 nm. The synergy of enhanced proton reduction and improved hole oxidation is proposed to account for the markedly increased activity. Our findings may provide a promising and facile approach to highly efficient photocatalysis for solar-energy conversion.

Enhanced gas and plasticizer barrier HTPB composite liner implanted with parallel orientation Fe3O4/RGO nanosheets by an ultrasound/magnet-coassisted method.

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-Selective Etching of Heterophase Au Nanostructures.

Selective oxidative etching is one of the most effective ways to prepare hollow nanostructures and nanocrystals with specific exposed facets. The mechanism of selective etching in noble metal nanostructures mainly relies on the different reactivity of metal components and the distinct surface energy of multimetallic nanostructures. Recently, phase engineering of nanomaterials (PEN) offers new opportunities for the preparation of unique heterostructures, including heterophase nanostructures. However, the synthesis of hollow multimetallic nanostructures based on crystal-phase-selective etching has been rarely studied. Here, a crystal-phase-selective etching method is reported to selectively etch the unconventional 4H and 2H phases in the heterophase Au nanostructures. Due to the coating of Pt-based alloy and the crystal-phase-selective etching of 4H-Au in 4H/face-centered cubic (fcc) Au nanowires, the well-defined ladder-like Au@PtAg nanoframes are prepared. In addition, the 2H-Au in the fcc-2H-fcc Au nanorods and 2H/fcc Au nanosheets can also be selectively etched using the same method. As a proof-of-concept application, the ladder-like Au@PtAg nanoframes are used for the electrocatalytic hydrogen evolution reaction (HER) in acidic media, showing excellent performance that is comparable to the commercial Pt/C catalyst.

N, S Co-Coordinated Zinc Single-Atom Catalysts for N-Alkylation of Aromatic Amines with Alcohols: The Role of S-Doping in the Reaction.

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.

Preparation of Amorphous SnO2 -Encapsulated Multiphased Crystalline Cu Heterostructures for Highly Efficient CO2 Reduction.

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.

Amido-Functionalized Magnetic Metal-Organic Frameworks Adsorbent for the Removal of Bisphenol A and Tetracycline.

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.