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1. Nitrogen-Doped Carbon Flowers with Fe and Ni Dual Metal Centers for Effective Electroreduction of Oxygen

   https://doi.org/10.3390/inorganics10030036  

   Mercado, Rene; Nichols, Forrest; Chen, Shaowei (March 2022, Inorganics)

   Carbon-based nanocomposites have been attracting extensive attention as high-performance catalysts in alkaline media towards the electrochemical reduction of oxygen. Herein, polyacrylonitrile nanoflowers are synthesized via a free-radical polymerization route and used as a structural scaffold and precursor, whereby controlled pyrolysis leads to the ready preparation of carbon nanocomposites (FeNi-NCF) doped with both metal (Fe and Ni) and nonmetal (N) elements. Transmission electron microscopy studies show that the FeNi-NCF composites retain the flower-like morphology, with the metal species atomically dispersed into the flaky carbon petals. Remarkably, despite a similar structure, elemental composition, and total metal content, the FeNi-NCF sample with a high Fe:Ni ratio exhibits an electrocatalytic performance towards oxygen reduction reaction (ORR) in alkaline media that is similar to that by commercial Pt/C, likely due to the Ni to Fe electron transfer that promotes the adsorption and eventual reduction of oxygen, as evidenced in X-ray photoelectron spectroscopic measurements. Results from this study underline the importance of the electronic properties of metal dopants in the manipulation of the ORR activity of carbon nanocomposites. 

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2. Oxygen Reduction Reaction Catalyzed by Metal-Nitrogen-Carbon Hybrids Derived from Metal-Organic Frameworks: Optimized Performance by Zinc Porogen

   Diniz, J.; Soe, E.; Lu, J. E.; Hauser, J.; Shaabani, A.; Oliver, S. R.; Chen, S. W. (December 2020, Science of advanced materials)

   null (Ed.)

   Carbon-based catalysts have been attracting extensive attention as viable candidates to replace platinum towards oxygen reduction reaction, a critical process at fuel cell cathode. An advancement has been the development of carbon-supported iron carbide (Fe3C/C) catalysts derived from the pyrolysis of metal organic frameworks (MOFs). In the present study, a series of Fe3C/C nanocomposites were prepared by controlled pyrolysis of FeMOF-NH2 with a systemic variation of the iron and zinc compositions in the MOF precursor. Scanning/transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopic measurements were carried out to examine the morphologies, structures, and elemental composition of the nanocomposites, while nitrogen adsorption/desorption and Raman studies were used to characterize the surface area and porosity. It was found that an optimal zinc to iron feeding ratio was required to produce a catalyst with a preferential pore size distribution. Electrochemical measurements revealed that the sample derived from 20% zinc replacement in the FeMOF-NH2 precursor exhibited the best electrocatalytic activity in alkaline media among the series, with the most positive onset potential and highest limiting current, which coincided with the highest surface area and porosity. The results suggest that deliberate structural engineering is critical in manipulating and optimizing the electrocatalytic activity of metal,nitrogen-codoped carbon nanocomposites. 

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3. Solution-phase synthesis and thermal conductivity of nanostructured CdSe, In ₂ Se ₃ , and composites thereof

   https://doi.org/10.1039/c5ta02755a  

   Ma, Yuanyu; Liu, Minglu; Jaber, Abbas; Wang, Robert Y. (January 2015, Journal of Materials Chemistry A)

   The use of nanoparticle-in-matrix composites is a common motif among a broad range of nanoscience applications and is of particular interest to the thermal sciences community. To explore this morphological theme, we create crystalline inorganic composites with nanoparticle volume fractions ranging from 0 to ∼100% using solution-phase processing. We synthesize these composites by mixing colloidal CdSe nanocrystals and In 2 Se 3 metal–chalcogenide complex (MCC) precursor in the solution-phase and then thermally transform the MCC precursor into a crystalline In 2 Se 3 matrix. We find rich structural and chemical interactions between the CdSe nanocrystals and the In 2 Se 3 matrix, including alterations in In 2 Se 3 grain size and orientation as well as the formation of a ternary phase, CdIn 2 Se 4 . The average thermal conductivities of the 100% In 2 Se 3 and ∼100% CdSe composites are 0.32 and 0.53 W m −1 K −1 , respectively. These thermal conductivities are remarkably low for inorganic crystalline materials and are comparable to amorphous polymers. With the exception of the ∼100% CdSe samples, the thermal conductivities of these nanocomposites are insensitive to CdSe volume fraction and are ∼0.3 W m −1 K −1 in all cases. We attribute this insensitivity to competing effects that arise from structural morphology changes during composite formation. This insensitivity to CdSe volume fraction also suggests that very low thermal conductivities can be reliably achieved using this solution-phase route to nanocomposites. 

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4. Multiwalled carbon nanotubes as hard templates to yield advanced geopolymer-based self-assembled nanostructured ceramics

   https://doi.org/10.1016/j.mechrescom.2023.104216  

   Xu, Yunzhi; Lee, Haklae; Buettner, Nathanial; Akono, Ange-Therese (December 2023, Mechanics Research Communications)

   Novel multifunctional construction materials are needed to promote resilient infrastructure in the face of climate change and extreme weather. Nanostructured materials such as geopolymer reinforced with carbon-based nanomaterials are a promising way to reach that goal. In recent years, several studies have investigated the influence of nanomaterials on the physical properties of geopolymer composites such as compressive strength and fracture toughness. Yet, a fundamental understanding of the influence of nanomaterials on the nanoscale and micron-scale structure has been elusive so far. Our research objective is to understand how multiwalled carbon nanotubes (MWCNT) can help tailor the microstructure of geopolymers to yield architected multifunctional nanocomposites. We synthesized geopolymer nanocomposites reinforced with 50-nm thick multiwalled carbon nanotubes with mass fractions in the range of 0.1 wt%, 0.2 wt%, and 0.5 wt%. Our major finding is that MWCNTs act as hard templates that promote geopolymer formation via self-assembly. Geopolymer nanoparticle growth is observed along the walls of MWCNTs. A refinement in grain size is observed: increasing the fraction of MWCNTs by 0.5 wt% leads to a reduction in grain size by 54%. Similarly, increasing the mass fraction of MWCNTs leads to a densification of the geopolymer matrix as demonstrated by the Fourier transform infrared spectroscopy results and the statistical deconvolution analysis. Mercury intrusion porosimetry shows a nanoscale tailoring of the pore size distribution: a 26% decrease in porosity is observed as the fraction of MWCNTs is increased to 0.5 wt%. As a result of these nanoscale structural changes, a greater resistance to long-term deformation is observed for MWCNT-reinforced geopolymers, as the creep modulus increases both locally and macroscopically. At the macroscopic level, a 42% increase in the macroscopic logarithmic creep modulus is observed as the fraction of MWCNTs is increased to 0.5 wt%. These findings and the supporting methodology are important to understand how to manipulate matter below 100 nm. This research also paves the way for the design of resilient infrastructure materials with tailored microstructure and mechanical properties. 

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5. Remarkably improved electrochemical hydrogen storage by multi-walled carbon nanotubes decorated with nanoporous bimetallic Fe–Ag/TiO ₂ nanoparticles

   https://doi.org/10.1039/C8DT03897J  

   Akbarzadeh, Raziyeh; Ghaedi, Mehrorang; Nasiri Kokhdan, Syamak; Vashaee, Daryoosh (January 2019, Dalton Transactions)

   Nanoporous bimetallic Fe–Ag nanoparticles (NPs) were synthesized using a facile chemical reduction method and used to decorate the surface of multi-walled carbon nanotubes (MWCNTs) for hydrogen sorption and storage. The effect of TiO 2 nanoparticles on the hydrogen storage properties of Fe–Ag/CNTs was further studied in detail. For this purpose, several nanocomposites of nanoporous bimetallic Fe–Ag/TiO 2 nanoparticles with different amounts of bimetallic Fe–Ag NPs were prepared via a hydrothermal method. The hydrogen storage capacity of the as-prepared nanocomposites was studied using electrochemical methods. The Fe–Ag/TiO 2 /CNT nanocomposite with 0.04 M bimetallic Fe–Ag NPs showed the highest capacity for hydrogen storage, which was ∼5× higher than that of pristine MWCNTs. The maximum discharge capacity was 2931 mA h g −1 , corresponding to a 10.94 wt% hydrogen storage capacity. Furthermore, a 379% increase in discharge capacity was measured after 20 cycles. These results show that Fe–Ag/TiO 2 /CNT electrodes display superior cycling stability and high reversible capacity, which is attractive for battery applications. 

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