Preparation of highly dispersed Ni single-atom doped ultrathin g-C3N4 nanosheets by metal vapor exfoliation for efficient photocatalytic CO2 reduction.

Single-atom photocatalysts can modulate the utilization of photons and facilitate the migration of photogenerated carriers. However, the preparation of single-atom uniformly doped photocatalysts is still a challenging topic. Herein, we propose the preparation of Ni single-atom doped g-C3N4 photocatalysts by metal vapor exfoliation. The Ni vapor produced by calcining nickel foam at high temperature accumulates in between g-C3N4 layers and poses a certain vapor pressure to destroy the interlayer van der Waals forces of g-C3N4. Individual metal atoms are doped into the structure while exfoliating g-C3N4 into nanosheets by metal vapor. Upon optimization of Ni content, the Ni single atom doped g-C3N4 nanosheets with 2.81 wt% Ni exhibits the highest CO2 reduction performance in the absence of sacrificial agents. The generation rates of CO and CH4 are 19.85 and 1.73 µmol g-1h-1, respectively. The improved photocatalytic performance is attributed to the anchoring Ni of single atoms on g-C3N4 nanosheets, which increases both carrier separation efficiency and reaction sites. This work provides insight into the design of photocatalysts with highly dispersed single-atom.

Boosting Benzene Oxidation with a Spin-State-Controlled Nuclearity Effect on Iron Sub-Nanocatalysts.

A fundamental understanding of the nature of nuclearity effects is important for the rational design of superior sub-nanocatalysts with low nuclearity, but remains a long-standing challenge. Using atomic layer deposition, we precisely synthesized Fe sub-nanocatalysts with tunable nuclearity (Fe1 -Fe4 ) anchored on N,O-co-doped carbon nanorods (NOC). The electronic properties and spin configuration of the Fe sub-nanocatalysts were nuclearity dependent and dominated the H2 O2 activation modes and adsorption strength of active O species on Fe sites toward C-H oxidation. The Fe1 -NOC single atom catalyst exhibits state-of-the-art activity for benzene oxidation to phenol, which is ascribed to its unique coordination environment (Fe1 N2 O3 ) and medium spin state (t2g 4 eg 1 ); turnover frequencies of 407 h-1 at 25 °C and 1869 h-1 at 60 °C were obtained, which is 3.4, 5.7, and 13.6 times higher than those of Fe dimer, trimer, and tetramer catalysts, respectively.

Pt Single Atoms on CrN Nanoparticles Deliver Outstanding Activity and CO Tolerance in the Hydrogen Oxidation Reaction.

The large-scale application of proton exchange membrane fuel cells is currently hampered by high cost of commercial Pt catalysts and their susceptibility to poisoning by CO impurities in H2 feed. In this context, the development of CO-tolerant electrocatalysts with high Pt atom utilization efficiency for hydrogen oxidation reaction (HOR) is of critical importance. Herein, Pt single atoms are successfully immobilized on chromium nitride nanoparticles by atomic layer deposition method, denoted as Pt SACs/CrN. Electrochemical tests establish Pt SACs/CrN to be a very efficient HOR catalyst, with a mass activity that is 5.7 times higher than commercial PtRu/C. Strikingly, the excellent performance of Pt SACs/CrN is maintained after introducing 1000 ppm of CO in H2 feed. The excellent CO-tolerance of Pt SACs/CrN is related to weaker CO adsorption on Pt single atoms. This work provides guidelines for the design and construction of active and CO-tolerant catalysts for HOR.

Rational construction of porous N-doped Fe2O3 films on porous graphene foams by molecular layer deposition for tunable microwave absorption.

Graphene-based materials with porous microstructure have attracted immense attentions due to their wide application in microwave absorption. However, constructing magnetic film with both porous microstructure and uniform pore size by using traditional methods still remains a challenge. To overcome this problem, we reported a facile strategy of molecular layer deposition (MLD) for successfully fabrication of the hybrid-architecture of porous graphene foams and nitrogen-doped porous Fe2O3 films. The surfaces of porous graphene foams are uniformly covered by porous Fe2O3 films without aggregation and the pore structures are widely distributed. The porous graphene-based composites exhibit remarkably enhanced microwave absorption performance compared to the pristine graphene foams. The minimum reflection loss value is increased by approximately 8 times, reaching -64.36 dB with a thickness of only 2.18 mm. More importantly, the absorption property can be precisely modulated by tuning the MLD cycle numbers and effective absorption bandwidth covers 3.04-18.0 GHz by adjusting the thickness from 1.0 to 5.0 mm. This work provides new insights for exploring novel and high-performance graphene-based microwave absorbents and offers a new idea to rationally design three-dimensional composites with porous magnetic films.

Conductive Polymer-Inorganic Hybrid Materials through Synergistic Mutual Doping of the Constituents.

Polymer-matrix-based inorganic-organic hybrid materials are at the cutting edge of current research for their great promise of merging properties of soft and hard solids in one material. Infiltration of polymers with vapors of reactive metal organics is a pathway for postsynthetic blending of the polymer with inorganic materials. Here, we show that this process is also an excellent method for fabricating conductive hybrid materials. Polyaniline (PANI) was infiltrated with ZnO and the initially insulating polymer was converted to a PANI/ZnO hybrid with conductivities as high as 18.42 S/cm. The conductivity is based on a synergistic effect of the constituting materials, where the inorganic and the polymeric fractions mutually act as dopants for the counterpart. The process temperature is a very important factor for successful infiltration, and the number of applied infiltration cycles allows tuning the level of conductivity of the resulting PANI/ZnO.

Porous TiO2 Nanotubes with Spatially Separated Platinum and CoOx Cocatalysts Produced by Atomic Layer Deposition for Photocatalytic Hydrogen Production.

Efficient separation of photogenerated electrons and holes, and associated surface reactions, is a crucial aspect of efficient semiconductor photocatalytic systems employed for photocatalytic hydrogen production. A new CoOx /TiO2 /Pt photocatalyst produced by template-assisted atomic layer deposition is reported for photocatalytic hydrogen production on Pt and CoOx dual cocatalysts. Pt nanoclusters acting as electron collectors and active sites for the reduction reaction are deposited on the inner surface of porous TiO2 nanotubes, while CoOx nanoclusters acting as hole collectors and active sites for oxidation reaction are deposited on the outer surface of porous TiO2 nanotubes. A CoOx /TiO2 /Pt photocatalyst, comprising ultra-low concentrations of noble Pt (0.046 wt %) and CoOx (0.019 wt %) deposited simultaneously with one atomic layer deposition cycle, achieves remarkably high photocatalytic efficiency (275.9 µmol h-1 ), which is nearly five times as high as that of pristine TiO2 nanotubes (56.5 µmol h-1 ). The highly dispersed Pt and CoOx nanoclusters, porous structure of TiO2 nanotubes with large specific surface area, and the synergetic effect of the spatially separated Pt and CoOx dual cocatalysts contribute to the excellent photocatalytic activity.

NiO/nanoporous graphene composites with excellent supercapacitive performance produced by atomic layer deposition.

Nickel oxide (NiO) is a promising electrode material for supercapacitors because of its low cost and high theoretical specific capacitance of 2573 F g(-1). However, the low electronic conductivity and poor cycling stability of NiO limit its practical applications. To overcome these limitations, an efficient atomic layer deposition (ALD) method is demonstrated here for the fabrication of NiO/nanoporous graphene (NG) composites as electrode materials for supercapacitors. ALD allows uniform deposition of NiO nanoparticles with controlled sizes on the surface of NG, thus offering a novel route to design NiO/NG composites for supercapacitor applications with high surface areas and greatly improved electrical conductivity and cycle stability. Electrochemical measurements reveal that the NiO/NG composites obtained by ALD exhibited excellent specific capacitance of up to ∼ 1005.8 F g(-1) per mass of the composite electrode (the specific capacitance value is up to ∼ 1897.1 F g(-1) based on the active mass of NiO), and stable performance after 1500 cycles. Furthermore, electrochemical performance of the NiO/NG composites is found to strongly depend on the size of NiO nanoparticles.

Microwave absorption properties of carbon nanocoils coated with highly controlled magnetic materials by atomic layer deposition.

In this work, atomic layer deposition is applied to coat carbon nanocoils with magnetic Fe(3)O(4) or Ni. The coatings have a uniform and highly controlled thickness. The coated nanocoils with coaxial multilayer nanostructures exhibit remarkably improved microwave absorption properties compared to the pristine carbon nanocoils. The enhanced absorption ability arises from the efficient complementarity between complex permittivity and permeability, chiral morphology, and multilayer structure of the products. This method can be extended to exploit other composite materials benefiting from its convenient control of the impedance matching and combination of dielectric-magnetic multiple loss mechanisms for microwave absorption applications.

Fabrication of nanostructured metal nitrides with tailored composition and morphology.

Unprecedented multi-channel TiN micro/nanotubes as well as various metal nitride nanofibers, including TiN, VN, NbN and ternary metal nitride nanofibers, were fabricated by a template free electrospinning method combined with post-nitridation.

Hydrophilic TiO2 porous spheres anchored on hydrophobic polypropylene membrane for wettability induced high photodegrading activities.

TiO(2) porous nanospheres on polypropylene (PP) films (TiO(2)/PP composite) are produced at ambient temperature. Particle/pore size match up is the key anchoring point to overcome the low affinity between hydrophilic materials and hydrophobic materials. With the hydrophilic TiO(2) catalyst evenly dispersed on a hydrophobic surface, the aqueous solution will selectively skip the substrate and wet the catalysts. Such a wettability-induced smart system maximizes the degrading activity of the TiO(2) catalyst. In photodegrading reactions, the resulting TiO(2)/PP composite film exhibits a 10 times higher activity in flow-type setup than the same TiO(2) catalyst in a traditional batch-type setup.