Metal-loaded polyol-montmorillonite with improved affinity towards hydrogen

Metal-organoclays (MOC) were prepared through incorporation of Boltorn polyol dendrimer H30 in Na⁺-exchanged montmorillonite (NaMt), followed by in-situ dispersion of Cu⁰ and Pd⁰ nanoparticles (CuNPs and PdNPs). The organoclays displayed high CO₂ retention capacity (CRC) of 3.6–11.1 μmol/g, but metal incorporation induced a significant increase of hydrogen uptake up to 51.8–508.2 micmol/g at the expense of the CRC. Thermal programmed desorption and FT-IR investigations revealed strong interactions with CO₂ before metal incorporation. These interactions markedly depleted in the presence of CuNPs and PdNPs. This was regarded as a precise indicator of the appreciable metal stabilization within the organic entanglement, due to enhancements of HO:Cu⁰ and HO:Pd⁰ interactions at the expense of HO:CO₂ carbonate-like association. The CO₂ and H₂ retention capacities (CRC and HRC, respectively) were found to strongly correlate to the number of OH groups of the dendritic moiety incorporated. Hydrogen retention appears to involve mainly physical interactions as supported by easy gas release between 20 °C and 75 °C or even at room temperature under vacuum. This demonstrates unequivocally the reversible capture of hydrogen. The increase of the hydrogen uptake with increasing contact time provides evidence of the occurrence of diffusion phenomena. This was not observed with CO₂ before metal incorporation, suggesting a structure compaction that improves metal stabilization. This opens new prospects for hydrogen storage via truly reversible capture on low cost clay materials and biodegradable hyperbranched macromolecules deriving from plants.     

黑曜岩添加膨润土尾矿制烧结饰面砖的工艺研究

利用黑曜岩中添加适量蒙脱石黏结料生产烧结饰面砖 ,通过试验找出生产烧结饰面砖的工艺参数 ,坯料成型水分 15 % ,成型压力 1 4MPa ,烧成温度 960～ 10 5 0℃。经测试 ,烧结制品的各项性能指标均高于GB5 10 1-1998国家标准     

大青山东段火山成因膨润土矿床中蒙脱石的矿物学特征研究

本文通过对大青山不同成因类型的膨润土矿床中蒙脱石矿物学特征的详细研究，揭示了蒙脱石的一系列矿物性质间的联系，包括X射线衍射特征、晶体化学特征、差热分析特征。同时，探讨了不同类型蒙脱石（切脱型、过渡到、怀俄明型）与矿床成因类型、成矿原岩的依存关系。     

Ruthenium nanoparticles immobilized in montmorillonite used as catalyst for methanolysis of ammonia borane

Ammonia borane (AB) is an intriguing molecular crystal material with extremely high hydrogen density. In the present study, we prepared ruthenium (Ru) nanoparticles immobilized in montmorillonite (MMT) and examine its catalytic effect on the methanolysis reaction of AB. The Ru/MMT catalyst was prepared by cation-exchange method followed by hydrogen reduction at elevated temperatures. Property examinations found that the Ru/MMT catalyst was highly effective and robust for promoting the methanolysis reaction of AB. For example, the methanolysis system employing Ru/MMT catalyst exhibited an average hydrogen generation rate of 29 L min⁻¹ g⁻¹ (Ru). The catalyst at its twentieth usage retained 95% of its initial activity and ensured 100% conversion of AB. Kinetics studies found that the methanolysis reaction of AB employing Ru/MMT catalyst follows first-order kinetics with respect to AB concentration and catalyst amount, respectively.     

Freezing–thawing effects on the properties of dialdehyde carboxymethyl cellulose crosslinked gelatin-MMT composite films

Freezing–thawing is used as a new method to disperse montmorillonite (MMT) in dialdehyde carboxymethyl cellulose (DCMC) crosslinked gelatin-based films. The effects of freezing–thawing on the structure and properties of gelatin-DCMC-MMT films were investigated. The data of XRD indicate that freezing–thawing plays an important role in dispersing MMT into gelatin matrix and reducing the nanoparticles aggregation. The optical properties studies show that gelatin-DCMC-MMT films are very transparent and have excellent barrier properties against UV light. Freezing–thawing process decreases the transparency of films at visible region due to the better dispersion of MMT. The resulting films exhibit similar total soluble matter (TSM) values. However, the films prepared by freezing–thawing method have higher moisture content (MC), may be resulting from the more void volume obtained during the freezing–thawing process. The water vapor permeability (WVP) measurements show that the addition of MMT decreases the WVP of the films. Moreover, the freezing–thawing method can further decrease the WVP of the films. In addition, the films prepared by freezing–thawing are observed with better mechanical properties and thermal stability. The results suggest that the freezing–thawing method is beneficial to dispersing MMT into the gelatin matrix and raising the properties of DCMC crosslinked gelatin-MMT films.     

Hydrogen wettability of clays: Implications for underground hydrogen storage

This study investigates the ability of hydrogen (H₂) to wet clay surfaces in the presence of brine, with implications for underground hydrogen storage in clay-containing reservoirs. Rather than measuring contact angles directly with hydrogen gas, a suite of other gases (carbon dioxide (CO₂), argon (Ar), nitrogen (N₂), and helium (He)) were employed in the gas-brine-clay system under storage conditions (moderate temperature (333 K) and high pressures (5, 10, 15, and 20 MPa)), characteristic of a subsurface environment with a shallow geothermal gradient. By virtue of analogies to H₂ and empirical correlations, wettabilities of hydrogen on three clay surfaces were mathematically derived and interpreted. The three clays were kaolinite, illite, and montmorillonite and represent 1:1, 2:1 non-expansive, and 2:1 expansive clay groups, respectively. All clays showed water-wetting behaviour with contact angles below 40° under all experimental set-ups. It follows that the presence of clays in the reservoir (or caprock) is conducive to capillary and/or residual trapping of the gas. Another positive inference is that any tested gas, particularly nitrogen, is suitable as cushion gas to maintain formation pressure during hydrogen storage because they all turned out to be more gas-wetting than hydrogen on the clay surfaces; this allows easier displacement and/or retrieval of hydrogen during injection/production. One downside of the predominant water wettability of the clays is the upstaged role of biogeochemical reactions at the wetted brine-clay/silicate interface and their potential to affect porosity and permeability. Water-wetting decreased from kaolinite as most water-wetting clay over illite to montmorillonite as most hydrogen-wetting clay. Their wetting behaviour is consistent with molecular dynamic modelling that establishes that the accessible basal plane of kaolinite's octahedral sheet is highly hydrophilic and enables strong hydrogen bonds whereas the same octahedral sheet in illite and montmorillonite is not accessible to the brine, rendering these clays less water-wetting.     

Montmorillonite-hybridized g-C3N4 composite modified by NiCoP cocatalyst for efficient visible-light-driven photocatalytic hydrogen evolution by dye-sensitization

The photocatalytic hydrogen evolution performance of g-C₃N₄ was enhanced via the hybridization with montmorillonite (MMT) and using NiCoP as cocatalyst. The highest hydrogen-evolution rate from water splitting under visible-light irradiation observed over MMT/g-C₃N₄/15%NiCoP was 12.50 mmol g⁻¹ h⁻¹ under 1.0 mmol L⁻¹ of Eosin Y-sensitization at pH of 11, which was ∼26.0 and 1.6 times higher than that of MMT/g-C₃N₄ (0.48 mmol g⁻¹ h⁻¹) and g-C₃N₄/15%NiCoP (7.69 mmol g⁻¹ h⁻¹). The apparent quantum yield at 420 nm reached 40.3%. The remarkably improved photocatalytic activity can be ascribed to the increased dispersion of g-C₃N₄ layers, staggered conduction band potentials between g-C₃N₄ and NiCoP, as well as the electrostatic repulsion originated from negatively charged MMT. This work demonstrates that MMT can be an outstanding support for the deposition of catalytically active components for photocatalytic hydrogen production.     

Preparation and characterization of Ni catalysts supported on pillared nanoporous bentonite powders for dry reforming reaction

The Ni/pillared-bentonite catalysts with high BET area were synthesized and used in dry reforming reaction. The effects of different parameters such as calcination temperature, OH⁻/Al³⁺ ratio, temperature and time of pillaring process and the content of nickel on the textural and catalytic properties of the synthesized catalysts were studied. The results indicated that the 15 wt% Ni catalyst supported on pillared bentonite prepared under specified conditions (OH⁻/Al³⁺ = 2.2, pillaring temperature of 40 °C and pillaring time of 3 h) possessed the highest BET area (90.80 m²/g). Also, this catalyst possessed higher catalytic activity and stability with lower amount of deposited carbon in comparison to other prepared catalysts in methane reforming with CO₂.     

Direct methanol fuel cell (DMFC) based on PVA/MMT composite polymer membranes

A novel composite polymer electrolyte membrane composed of a PVA polymer host and montmorillonite (MMT) ceramic fillers (2–20 wt.%), was prepared by a solution casting method. The characteristic properties of the PVA/MMT composite polymer membrane were investigated using thermal gravimetric analysis (TGA), differential scanning calorimetry (DSC), dynamic mechanical analysis (DMA), scanning electron microscopy (SEM), and micro-Raman spectroscopy, and the AC impedance method. The PVA/MMT composite polymer membrane showed good thermal and mechanical properties and high ionic conductivity. The highest ionic conductivity of the PVA/10 wt.%MMT composite polymer membrane was 0.0368 S cm⁻¹ at 30 °C. The methanol permeability (P) values were 3–4 × 10⁻⁶ cm² s⁻¹, which was lower than that of Nafion 117 membrane of 5.8 × 10⁻⁶ cm² s⁻¹. It was revealed that the addition of MMT fillers into the PVA matrix could markedly improve the electrochemical properties of the PVA/MMT composite membranes; which can be accomplished by a simple blend method. The maximum peak power density of the DMFC with the PtRu anode based on Ti-mesh in a 2 M H₂SO₄ + 2 M CH₃OH solution was 6.77 mW cm⁻² at ambient pressure and temperature. As a result, the PVA/MMT composite polymer appears to be a good candidate for the DMFC applications.     

Production of high porosity nanoparticles of cerium oxide in clay

Cerium oxide nanoparticles modified montmorillonite was obtained by interaction of a clay with (NH₄)₂Ce(NO₃)₆. The mean size of cerium oxide nanoparticles in clay was at 3.5 nm. The product was an amorphous solid and showed high permanent porosity and stability at high temperatures. The amorphous structure of the sample was proven by X-ray diffraction and electronic diffraction. The porous structure was studied by means of chemisorption and it was shown that samples calcined at 550 °C had S_BET = 239 m²/g; micropore volume = 0.1839 cm³/g; average pore diameter = 3.07 nm.