MOF (UiO-66-NH2)@COF (TFP-TABQ) hybrids via on-surface condensation reactions for sustainable energy storage.

Core-shell MOF@COF hybrids were synthesized via subsequent modification of MOF UiO-66-NH2 with 1,3,5-triformylphloroglucinol (TFP) and 2,3,5,6-tetraaminobenzoquinone (TABQ). The hybrids exhibited significant surface area (236 m2 g-1) and outstanding electrochemical performance (103 F g-1 at 0.5 A g-1), surpassing both COFs and MOFs, thereby showcasing the potential of on-surface condensation reactions for developing high-performance energy storage devices.

Co-Existence of Iron Oxide Nanoparticles and Manganese Oxide Nanorods as Decoration of Hollow Carbon Spheres for Boosting Electrochemical Performance of Li-Ion Battery.

Here, we report that mesoporous hollow carbon spheres (HCS) can be simultaneously functionalized: (i) endohedrally by iron oxide nanoparticle and (ii) egzohedrally by manganese oxide nanorods (FexOy/MnO2/HCS). Detailed analysis reveals a high degree of graphitization of HCS structures. The mesoporous nature of carbon is further confirmed by N2 sorption/desorption and transmission electron microscopy (TEM) studies. The fabricated molecular heterostructure was tested as the anode material of a lithium-ion battery (LIB). For both metal oxides under study, their mixture stored in HCS yielded a significant increase in electrochemical performance. Its electrochemical response was compared to the HCS decorated with a single component of the respective metal oxide applied as a LIB electrode. The discharge capacity of FexOy/MnO2/HCS is 1091 mAhg-1 at 5 Ag-1, and the corresponding coulombic efficiency (CE) is as high as 98%. Therefore, the addition of MnO2 in the form of nanorods allows for boosting the nanocomposite electrochemical performance with respect to the spherical nanoparticles due to better reversible capacity and cycling performance. Thus, the structure has great potential application in the LIB field.

Boosting of photocatalytic hydrogen evolution via chlorine doping of polymeric carbon nitride.

Chlorine is found to be a suitable element for the modification of polymeric carbon nitride properties towards an efficient visible-light photocatalytic activity. In this study, chlorine-doped polymeric carbon nitride (Cl-PCN) has been examined as a photocatalyst in the hydrogen evolution reaction. The following aspects were found to enhance the photocatalytic efficiency of Cl-PCN: (i) unique location of Cl atoms at the interlayers of PCN instead of on its π-conjugated planes, (ii) slight bandgap narrowing, (iii) lower recombination rate of the electron-hole pairs, (iv) improved photogenerated charge transport and separation, and (v) higher reducing ability of the photogenerated electrons. The above factors affected the 4.4-fold enhancement of the photocatalytic efficiency in hydrogen evolution in comparison to the pristine catalyst.

The impact of environmental water on the potential application of core-shell titania-silica nanospheres as photocatalysts.

In this study, the core-shell silica nanospheres modified with titanium dioxide were tested in the photocatalytic decomposition of dyes. The presented data underlines the advantages and shortcomings in the potential application of silica-based catalysts to neutralize organic pollutants. During the photocatalytic reaction in distilled water, catalysts showed decreased efficiency due to a carbon layer deposited on its surface. This finding set an additional goal to investigate the possibility of regenerating the photocatalyst. Studies have shown that the catalyst could be successfully reused following the thermal removal of deposited carbon.Furthermore, the reactivated silica-titania catalysts exhibited comparable photocatalytic performance to the newly made nanomaterial. Surprisingly, catalyst application in the river water eventually resulted in the permanent deactivation of silica-titania nanospheres, which was caused by the interchangeable silica dissolution/precipitation process on the surface of the studied nanomaterial. In environmental water, silica dissolves and precipitates on titanium dioxide's surface, blocking the interaction between organic compounds and TiO2. The deactivation occurring in the environmental samples is irreversible. In distilled water, the decomposition of organic compounds leads to photocatalysts' deactivation by forming a carbon layer on their surface. Reactivation of the silica-based photocatalyst after distilled water is achievable by annealing at a high temperature. In light of our findings, the combination of the photocatalytic properties of TiO2and the silica template shows no prospects in the purification of polluted waste or environmental water.

Two-Dimensional Molybdenum Diselenide Tuned by Bimetal Co/Ni Nanoparticles for Oxygen Evolution Reaction.

Herein, we report fabrication of MoSe2 functionalized with bimetal Co/Ni particles, which shows promising electrochemical performance in oxygen and hydrogen evolution reactions (OER and HER) due to its physicochemical properties such as electronic configuration and great electrochemical stability. We propose functionalization with two transition metals, cobalt and nickel, expecting a synergic effect in electrocatalytic activity in a water splitting reaction. These electrocatalytic reactions are essential for efficient electrochemical energy storage. The thin flakes were obtained by exfoliation of bulk molybdenum diselenide. Next, after deposition of metals, precursors were carbonized. Electrochemical data reveal that the presence of Ni and Co particles boosts electrocatalyst performance, providing a great number of active sites due to their conductivity. Interestingly, the material exhibited great evolution potential and good stability in long-term tests.

Spinel of Nickel-Cobalt Oxide with Rod-Like Architecture as Electrocatalyst for Oxygen Evolution Reaction.

The renewable energy technologies require electrocatalysts for reactions, such as the oxygen and/or hydrogen evolution reaction (OER/HER). They are complex electrochemical reactions that take place through the direct transfer of electrons. However, mostly they have high over-potentials and slow kinetics, that is why they require electrocatalysts to lower the over-potential of the reactions and enhance the reaction rate. The commercially used catalysts (e.g., ruthenium nanoparticles-Ru, iridium nanoparticles-Ir, and their oxides: RuO2, IrO2, platinum-Pt) contain metals that have poor stability, and are not economically worthwhile for widespread application. Here, we propose the spinel structure of nickel-cobalt oxide (NiCo2O4) fabricated to serve as electrocatalyst for OER. These structures were obtained by a facile two-step method: (1) One-pot solvothermal reaction and subsequently (2) pyrolysis or carbonization, respectively. This material exhibits novel rod-like morphology formed by tiny spheres. The presence of transition metal particles such as Co and Ni due to their conductivity and electron configurations provides a great number of active sites, which brings superior electrochemical performance in oxygen evolution and good stability in long-term tests. Therefore, it is believed that we propose interesting low-cost material that can act as a super stable catalyst in OER.

Well-Designed Porous Graphene Flakes for Lithium-Ion Batteries with Outstanding Rate Performance.

Porous graphene flakes (PGFs) with controllable pore sizes are selectively prepared through self-assembly of Fe3O4 nanoparticles on organic modified montmorillonite combined with carbonization and subsequent annealing treatment. The resulting PGFs with a thickness of 5 nm have a specific surface area of 337 m2/g, pore volume of 0.66 cm3/g, and mean pore diameter of 15 nm. Due to their unique porous flake structures, PGFs show an impressive rate performance in lithium-ion batteries, especially at high current densities (238 mA h/g at 10 C) as well as long-term stability in comparison to the commercial graphite (55 mA h/g at 10 C). Therefore, PGFs with their key structural properties serve as ideal candidates as electrode components in lithium-ion batteries and show great potential application in other energy storage fields.

Graphitic Carbon Nitride and Titanium Dioxide Modified with 1 D and 2 D Carbon Structures for Photocatalysis.

Enhancing the photocatalytic performance of graphitic carbon nitride (g-C3 N4 , GCN) and titanium dioxide (TiO2 ) has played a key role in the energy and environmental protection research community. Therefore, it is necessary to explore the synergy of both materials with carbon nanostructures for photocatalysis. Among the variety of carbon materials, graphene flakes and nanotubes, as nanoadditives to improve electron charge transfer and the optical absorption behavior in the visible-light region, have been widely explored. Thus, flake-like (2 D) and tubular (1 D) carbon structures in composition with GCN and/or TiO2 are reviewed, as are their photocatalytic response. Current trends clearly indicate that this type of molecular hybrids can be efficiently exploited in this field. This Minireview covers state-of-the-art research over the period of 2015 to 2018.

MOF-5 derived carbon as material for CO2 absorption.

In our study we prepared MOF-5 derived carbon to reveal the thermodynamics of CO2 absorption processes in great detail. Porous carbon material was prepared from a metal-organic framework (MOF-5) via carbonization at 1000 °C. The obtained structure consists only of carbon and exhibits a BET specific surface area, total pore volume and micropore volume of 1884 m2 g-1, 1.84 cm3 g-1 and 0.59 cm3 g-1, respectively. Structural analysis allowed the assumption that this material is an ideal candidate for efficient CO2 absorption. The CO2 uptake was 2.43 mmol g-1 at 25 °C and 1 bar. Additionally, the absorption over a wide range of temperatures (25, 40, 60, 80 and 100 °C) and pressures (in range of 0-40 bar) was investigated. It is shown that the CO2 absorption isotherm fits a multitemperature Sips model. The calculated Sips equation parameters allows the isosteric heat of adsorption to be obtained. The isosteric heat of adsorption for CO2 decreased substantially with an increase in surface coverage by gas molecules. This indicates a negligible intermolecular interaction between CO2 molecules. A decrease in the isosteric heat of adsorption with surface coverage is a result of the disappearance of favourable adsorption sites.

Correction: MOF-5 derived carbon as material for CO2 adsorption.

[This corrects the article DOI: 10.1039/C9RA01786K.].

Poly(vinylidene fluoride) and Carbon Derivative Structures from Eco-Friendly MOF-5 for Supercapacitor Electrode Preparation with Improved Electrochemical Performance.

Electrodes from carbonized Zn4O(1,4-benzodicarboxylic acid) (MOF-5) structures were prepared successfully via evaporating the solvent with a poly(vinylidene fluoride) (PVDF) binder. The solvent used for a nanocomposite cast was easily removed. Such an elegant method for preparing electrodes provides a facile, cost-effective, and void/cracking-free nanocomposite distribution on the current collector. The highly porous nanoparticles containing pure carbon attach well to the PVDF membrane which results in an increased active surface area of the electrode to 847 m²/g. The electrochemical analysis shows that the best weight ratio of CMOF-5 to PVDF equals 85:15, 80:20, and 75:25, respectively. The specific capacitance of these samples is 218 F/g, 210 F/g, and 180 F/g, correspondingly. An additional advantage of the electrode prepared from the carbonized MOF-5 is the possibility to synthesis MOF structures from recovered substrates used in its synthesis (distilled N,N-Dimethylformamide DMF and terephthalic acid recovered from polyethylene terephthalate waste). We will demonstrate this in this contribution as well. Furthermore, the carbonized MOF-5 can be recovered from the spent electrode and reused again in the electrochemical device.

From Hollow to Solid Carbon Spheres: Time-Dependent Facile Synthesis.

Here, we report a facile route for obtaining carbon spheres with fully tunable shell thickness. Using a hard template in chemical vapor deposition (CVD), hollow carbon spheres, solid carbon spheres, and intermediate structures can be obtained with optimized process time. The resulting carbon spheres with particle diameters of ~400 nm, as well as a controllable shell thickness from 0 to 70 nm, had high Brunauer⁻Emmett⁻Teller (BET) specific surface area (up to 344.8 m²·g-1) and pore volume (up to 0.248 cm³·g-1). The sphere formation mechanism is also proposed. This simple and reproducible technique can deliver carbon materials for various applications, e.g., energy storage and conversion, adsorption, catalytic, biomedical, and environmental applications.

A Comparison of Hydrogen Storage in Pt, Pd and Pt/Pd Alloys Loaded Disordered Mesoporous Hollow Carbon Spheres.

Comprehensive study to evaluate the ability of hydrogen uptake by disordered mesoporous hollow carbon spheres doped witch metal such as Pt, Pd or Pt/Pd was conducted. They were synthesized facilely using sonication and then calcination process under vacuum at the temperature of 550 °C. The effect on hydrogen sorption at neat-ambient conditions (40 °C, up to 45 bar) was thoroughly analyzed. The results clearly revealed that metal functionalization has a significant impact on the hydrogen storage capacity as the mechanism of gas uptake depends on two factors: metal type and certain size of particles. Thus, functionalized spheres adsorb hydrogen by physisorption forming metal hydrides or metal hydrides combined with hydrogen spillover effect. As a result, a sample with narrower distribution of nanoparticles and smaller specific size exhibited enhanced hydrogen uptake.