Metal–Organic Frameworks Based on Group 3 and 4 Metals

Metal–organic frameworks (MOFs) based on group 3 and 4 metals are considered as the most promising MOFs for varying practical applications including water adsorption, carbon conversion, and biomedical applications. The relatively strong coordination bonds and versatile coordination modes within these MOFs endow the framework with high chemical stability, diverse structures and topologies, and interesting properties and functions. Herein, the significant progress made on this series of MOFs since 2018 is summarized and an update on the current status and future trends on the structural design of robust MOFs with high connectivity is provided. Cluster chemistry involving Y, lanthanides (Ln, from La to Lu), actinides (An, from Ac to Lr), Ti, and Zr is initially introduced. This is followed by a review of recently developed MOFs based on group 3 and 4 metals with their structures discussed based on the types of inorganic or organic building blocks. The novel properties and arising applications of these MOFs in catalysis, adsorption and separation, delivery, and sensing are highlighted. Overall, this review is expected to provide a timely summary on MOFs based on group 3 and 4 metals, which shall guide the future discovery and development of stable and functional MOFs for practical applications.     

Design of a Multilayered Oxygen-Evolution Electrode with High Catalytic Activity and Corrosion Resistance for Saline Water Splitting

The realization of seawater electrolysis requires high-performing anode materials that should possess good catalytic activity, stability, and specificity for the oxygen evolution reaction (OER) as well as high resistance toward chloride corrosion. Herein, the design of a multilayered oxygen-evolution electrode is reported to meet the multiple needs of anode material for saline water splitting. The multilayered electrode is synthesized through direct thermal boronization of commercially available NiFe alloy plate with boron powder, followed by electrochemical oxidation. And this electrode is composed of the surface oxidized NiFeBx alloy layer, the NiFeBx alloy interlayer, and the NiFe alloy substrate. The boron species are present in the form of metaborate in the outermost oxidized NiFeBx layer, and their existence is conductive to the generation and stabilization of the catalytic active phase γ-(Ni,Fe)OOH. The introduction of NiFeBx interlayer effectively prevents the excessive oxidative corrosion of the anode material in the electrolyte containing chloride ions.     

Co3O4 nanoparticles decorated Polypyrrole/carbon nanocomposite as efficient bi-functional electrocatalyst for electrochemical water splitting

An effective bi-functional electrocatalyst of Co₃O₄/Polypyrrole/Carbon (Co₃O₄/Ppy/C) nanocomposite was prepared through a simple dry chemical method and used to catalyze the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). Three types of carbon support as Vulcan carbon, reduced graphite oxide (RGO) and multi-walled carbon nanotubes (MCNTs) were used to study the influence on electrochemical reactions. Spherical shaped Co₃O₄ nanoparticles with 8–10 nm was found uniformly distributed on Ppy/C composite, which were analyzed by X-ray diffraction and transmission electron microscopy techniques. Amongst, Co₃O₄/Ppy/MWCNT shows improved bifunctional electrocatalytic activity towards both OER and HER with relatively low over potential (340 mV vs. 490 mV at 10 mA cm⁻²) and Tafel slope (87 vs. 110 mV dec⁻¹). In addition to that, MWCNT supported Co₃O₄/Ppy nanocomposite exhibits good electronic conductivity and electrochemical stability up to 2000 potential cycles. The results clearly indicate that the Co₃O₄/Ppy/MWCNT nanocomposite could be the promising bi-functional electrocatalyst for efficient water electrolysis.     

Thermal annealing characteristics of solar selective absorber coatings based on nano-multilayered MoOx films

Designing double metal-dielectric (cermet) solar selective absorber coatings (SSACs) often requires complex co-sputtering techniques with multiple targets. This inevitably limits the simple and low-cost industrial fabrication. Here, we develop novel nano-multilayered MoO_x-based SSACs by simple and stable one-step reactive magnetron sputtering process using single molybdenum target. The proposed multilayer SSACs exhibit good solar absorptance of 0.93 and low thermal emittance of 0.06. Owing to the temperature-induced oxygen diffusion and oxidation phenomenon the as-sputtered SSACs have a poor thermal tolerance under air atmosphere, and after annealing at 200 °C for 150 h, the resulting absorptance is diminished from 0.93 to 0.90. However, the optical performance of the annealed SSAC is relatively stable in high-vacuum environment, even after annealing at 450 °C for 200 h, it still displays an ideal spectral selectivity of 0.92/0.07. With above properties, the resulting MoO_x-based SSAC is a promising absorber for enduring thermal harvesting in solar vacuum collectors.     

Effects of annealing on copper substrate surface morphology and graphene growth by chemical vapor deposition

Understanding the mechanism of graphene synthesis by chemical vapor deposition and the effect of process parameters is critical for production of high-quality graphene. In the present work, we investigated the effect of H₂ concentration during annealing on evolution of Cu surface morphology, and on deposited graphene characteristics. Our results revealed that H₂ had a smoothening effect on Cu surface as its surface roughness was reduced significantly at high H₂ concentration along with the formation of surface facets, dents and nanometer-sized particles. Furthermore, H₂ content influenced the graphene morphology and its quality. A low H₂ concentration (0% and 2.5%) during annealing promoted uniform and good quality bilayer graphene. In contrast, a high concentration of H₂ (20% and 50%) resulted in multilayer, non-uniform and defective graphene. Interestingly, the annealed Cu surface morphology differed considerably from that obtained after deposition of graphene, indicating that graphene deposition has its own impact on Cu surface.     

Fabrication and microwave absorption properties of magnetite nanoparticle–carbon nanotube–hollow carbon fiber composites

Absorbents with “tree-like” structures, which were composed of hollow porous carbon fibers (HPCFs) acting as “trunk” structures, carbon nanotubes (CNTs) as “branch” structures and magnetite (Fe₃O₄) nanoparticles playing the role of “fruit” structures were prepared by chemical vapor deposition technique and chemical reaction. Microwave reflection loss, permittivity and permeability of Fe₃O₄–CNTs–HPCFs composites were investigated in the frequency range of 2–18 GHz. It was proven that prepared absorbents possessed the excellent electromagnetic wave absorbing performances. The bandwidth with a reflection loss less than −15 dB covers a wide frequency range from 10.2 to 18 GHz with the thickness of 1.5–3.0 mm, and the minimum reflection loss is −50.9 dB at 14.03 GHz with a 2.5 mm thick sample layer. Microwave absorbing mechanism of the Fe₃O₄–CNTs–HPCFs composites is concluded as dielectric polarization and the synergetic interactions exist between Fe₃O₄ and CNTs–HPCFs.     

Enhanced visible light photocatalytic performance of Sb-doped (BiO)2CO3 nanoplates

Sb-doped (BiO)₂CO₃ nanoplates have been successfully fabricated via a facile hydrothermal method. XRD patterns, XPS spectra, SEM and TEM images demonstrated that doping with antimony (Sb) has no effect on the crystal phase, morphology and structure of (BiO)₂CO₃ nanoplates. However, the red shift of diffraction peak in the 2θ range of 29–32° was observed, which could be attributed to the substitution of larger radius of Bi atoms by lower radius of Sb atoms resulting in the decrease of lattice parameters. The photocatalytic performance of Sb-doped (BiO)₂CO₃ nanoplates was evaluated by the degradation of RhB upon visible light irradiation. It was found that the visible-light-induced photocatalytic activity of Sb-doped (BiO)₂CO₃ nanoplates was significantly improved, which was mainly attributed to its enhanced surface area and electron transfer rate. It was proposed that RhB photodegradation proceeded through a photosensitization pathway upon visible light irradiation.     

Fabrication of platinum thin films for ultra-high electrocatalytic hydrogen evolution reaction

While the noble metals (e.g., platinum, (Pt)) remain the benchmark electrocatalyst for the hydrogen evolution reaction (HER), their mass production require a reduced metal loading and faster fabrication protocols. The aim of the present work is to prepare Pt thin films by simple and fast fabrication technique, and to evaluate their performance for HER. The thin films of Pt are grown on two substrates, namely titanium foil (Ti) and nickel foam (NF), using a single step aerosol assisted chemical vapor deposition (AACVD) method. The film deposition time are varied from 20 to 60 min. Microscopic analyses suggest a gradual evolution of the films into percolated and/or porous nanostructures, a feature that remains highly desired to allow the maximum access of active sites. The performance of the as-prepared electrodes is evaluated by monitoring the HER in acidic electrolyte. The Pt film on nickel foam (Pt/NF) exhibits better electrical conductivity and smaller charge transfer resistance, while the film deposited on the Ti foil (Pt/Ti) demonstrates superior catalytic activity per active sites. The as-prepared Pt/Ti and Pt/NF electrodes produce 10 mA cm⁻² at overpotential of 28 mV and 26 mV, respectively, better in performance than commercial Pt/C electrode (~39 mV), set a new bench mark electrocatalyst for the HER.     

Single‐step synthesis of a radically polymerizable 1,1′‐bi‐2‐naphthol derivative for asymmetric catalysis

A new polymerizable 1,1′‐bi‐2‐naphthol derivative for polymer‐supported catalytic asymmetric synthesis is presented. The synthesis is conducted within a single reaction step, which is a major advantage over other approaches presented in the literature. The ligand‐bearing polymer is prepared through copolymerization with N‐isopropylacrylamide. Preliminary experiments on the utility in catalytic asymmetric alkylation reactions reveal the accessibility and activity of the polymer‐attached catalysts. The stereoselectivity of the reaction is found to be somewhat lower than for reactions performed in the presence of free 1,1′‐bi‐2‐naphthol, and thus requires further optimization. The enantiomeric excess of the reaction products was determined via ¹H NMR spectroscopy after chiral derivatization with (R)‐α‐methylbenzyl isocyanate. © 2015 Society of Chemical Industry     

Pt-based trimetallic nanocrystals with high proportions of M (M=Fe,Ni) metals for catalyzing oxygen reduction reaction

For boosting oxygen reduction reaction (ORR) in proton exchange membrane fuel cells (PEMFCs), a new type of multi-functional catalyst with high activity, high stability, and low cost has been designed and prepared by introducing high proportions of M (M = Fe, Ni) metals in Pt-based nanoparticles through a microwave-assisted polyol method, followed by thermal annealing process. A uniform dispersion of nanoparticles (5 nm) and a face-centered tetragonal (fct) phase improve the activity and stability of the Pt–Fe–Ni/C catalyst. Owing to differences in the surface energies of the alloying elements, Pt atoms with low surface energy have a tendency to segregate from the subsurface to the surface during the annealing. This tendency exposes the internal Pt atoms to the surface of the nanoparticles in the existence of high proportions of M metals, significantly improving the utilization of Pt. As a cathode catalyst, the Pt–Fe–Ni/C catalyst annealed at 675 °C with a mass activity of 0.73 A/mg_Pt, which is 3.5 times higher than that of the commercial Pt/C catalyst, exhibits an excellent half-cell performance. An accelerated durability test demonstrates that the prepared Pt–Fe–Ni/C-675 catalyst is more stable than the commercial Pt/C. The proposed multi-functional catalyst has great potential for PEMFCs and other applications.