Efficient utilization of silanol group in rice husk to promote the synthesis of Ni-phyllosilicate for CO2 methanation

It is a challenge to prepare Ni-phyllosilicate catalysts deriving from the reaction of nickel salts and biomass-based silica with high Ni contents. In order to efficiently synthesize nickel phyllosilicate, the acid-treated rice husk without calcination (P-R) was directly used as the raw material. The as-synthesized Ni-phyllosilicate (N/P-R) exhibited high nickel content of 46.7 wt% owing to utilization of the abundant silanol group in the fresh rice husk. On the contrary, the Ni content of Ni-phyllosilicate sample (N/R–S) prepared using the calcinated rice husk-based silica was only 4.8 wt% because of the loss of silanol group during calcination process. As a result, N/P-R displayed much higher catalytic activity for CO₂ methanation than N/R–S. It was found that the silanol group was in favour of forming the important intermediate Si(OH)₄, and thereby facilitated the formation of nickel phyllosilicate. In addition, the N/P-R catalyst demonstrated superior stability and excellent anti-sintering ability in the long lifetime test. In short, the proposed method in this work could not only efficiently synthesize nickel phyllosilicate with high Ni content, but also reduce energy consumption and operation steps compared to the one prepared using biomass-based silica.     

Nickel-based metal−organic framework-derived whisker-shaped nickel phyllosilicate toward efficiently enhanced mechanical,flammable and tribological properties of epoxy nanocomposites

Metal−organic framework-derived materials have attracted significant attention in the applications of functional materials. In this work, the rod-like nickel-based metal−organic frameworks were first synthesized and subsequently employed as the hard templates and nickel sources to prepare the whisker-shaped nickel phyllosilicate using a facile hydrothermal technology. Then, the nickel phyllosilicate whiskers were evaluated to enhance the mechanical, thermal, flammable, and tribological properties of epoxy resin. The results show that adequate nickel phyllosilicate whiskers can disperse well in the matrix, improving the tensile strength and elastic modulus by 13.6% and 56.4%, respectively. Although the addition of nickel phyllosilicate whiskers could not obtain any UL-94 ratings, it enhanced the difficulty in burning the resulted epoxy resin nanocomposites and considerably enhanced thermal stabilities. Additionally, it was demonstrated that such nickel phyllosilicate whiskers preferred to improve the wear resistance instead of the antifriction feature. Moreover, the wear rate of epoxy resin nanocomposites was reduced significantly by 80% for pure epoxy resin by adding 1 phr whiskers. The as-prepared nickel phyllosilicate whiskers proved to be promising reinforcements in preparing of high-performance epoxy resin nanocomposites.     

多级多孔硅酸镍微球的合成及其对碱性品红的高效吸附

层状硅酸镍因其独特的结构, 在电化学和催化等领域展现出良好的应用前景, 其合成与性能研究近年来受到广泛关注。本研究以氯化镍和正硅酸乙酯为原料, 采用水热法合成了硅酸镍微球, 并详细探究了镍硅比和碱源对产物组成、形貌及孔结构的影响。在优化条件下, 产物呈现由纳米片组装的、平均直径约为2.5 μm的微球形貌, 比表面积为119.6 m²·g^-1, 孔容为0.673 cm³·g^-1。Zeta电位分析表明, 该微球在pH=3~10范围内保持表面电负性。将硅酸镍微球用于处理碱性品红溶液, 吸附过程符合准二级动力学模型。在初始浓度为50 mg·L^-1的条件下, 吸附容量可达120.7 mg·g^-1, 脱除率达96.6%, 远优于改性粘土及近年来报道的多种材料。吸附量与平衡浓度的数据表明, 碱性品红在硅酸镍微球上的吸附符合Freundlich吸附模型, 1/n=0.1678, 表明该吸附为多层非均相吸附且吸附作用力强。     

Characterization of LDH (phyllosilicate/carbonate) type compounds formed in the pozzolanic reaction of phyllosilicate-rich industrial waste

Reutilization of industrial waste products as cement additives yields a number of secondary materials, yet their identification is not always trivial. Confirmation of the formation of a LDH-type (phyllosilicate/carbonate) material is the main purpose of this study. Mineralogically, organic and inorganic compounds form some industrial wastes, among which the phyllosilicates are prominent. Crystalline and amorphous hydrated phases appeared during the pozzolanic reaction in a dehydroxylated phyllosilicate/lime system, whose controlled activation yielded dehydroxylated products with high pozzolanic properties. The LDH-type (phyllosilicate/carbonate) material was one of the reaction products; this material could be considered as the superposition type 1:1 of tetrahedral layers of silicon and aluminum and octahedral layers of aluminum (dehydroxylated kaolinite), generating a positive charge in the interlaminar region compensated by carbonate anions with a basal spacing (001) measured by XRD at 7.57Å. Therefore, several techniques were used to determine whether they could be included in the structural group named Layered Double Hydroxides (LDHs), as they are, too, laminar layers of oxides and hydroxides with a positive laminar charge in the interlayer region compensated by the presence of anions with similar basal spacing. In this research, the effects of activation temperature and calcite proportion were analyzed on the hydrated phases formed after 28 days of pozzolanic reaction in a metakaolin (MK)/lime system. The MK was obtained from a mix of 1:1; 2:1 and 3:1 kaolinite:calcite mixture, thermally activated at 750°C for 2 hours, comparing it with kaolinite activated at 600°C for 2 hours. As the most LDH-rich sample, the 1:1 LDH-type (phyllosilicate/carbonate) phase was characterized using XRD, SEM-EDX, HRTEM-EDX, FTIR, NMR-MAS, and Raman spectroscopy.     

Sodic and Acidic Crystalline Lamellar Magadiite Adsorbents for the Removal of Methylene Blue from Aqueous Solutions: Kinetic and Equilibrium Studies

The present study reports the feasibility of two synthetic crystalline lamellar nano-silicates, sodic magadiite (Na-mag) and its converted acidic form (H-mag), as alternative adsorbents for the removal of the dye methylene blue (MB) from aqueous solutions. The ability of these adsorbents for removing the dye was explored through the batch adsorption procedure. Effects such as the pH and the adsorbent dosage on the adsorption capacities were explored. Four kinetic models were applied, the adsorption being best fitted to a fractionary-order kinetic model. The kinetic data were also adjusted to an intra-particle diffusion model to give two linear regions, indicating that the kinetics of adsorption follows multiple sorption rates. The equilibrium data were fitted to Langmuir, Freundlich, Sips, and Redlich-Peterson isotherm models. The maxima adsorption capacities for MB of Na-mag and H-mag were 331 and 173 mg g^?1, respectively.     

Modification of silica supported nickel catalysts with lanthanum for stability improvement in methane reforming with CO2

Dry reforming of methane (DRM) with excessive methane composition at CH₄/CO₂ = 1.2:1 was studied over lanthanum modified silica supported nickel catalysts (Ni-xLa-SiO₂, x: 1, 2, 4, and 6% in the target weight percent of La). The catalysts were prepared by ammonia evaporation method. Nickel phyllosilicate and La₂O₃ were the main phases in calcined catalysts. The modification of La enhanced the formation of 1:1 and Tran-2:1 nickel-phyllosilicate. There existed an optimum content of La loading at 1.50 wt% in Ni–2La–SiO₂ which resulted in its highest reduction degree (95.3%). The catalysts with appropriate amounts of La exhibited higher amount of CO₂ adsorption and created more medium and strong base centers. The sufficient number of exposed metallic nickel sites to catalyze the reforming reaction, as well as enough medium and strong basic sites in Ni–La–SiO₂ interface to accomplish the carbon removal were two important factors to attenuate catalyst deactivation. The catalyst stability evaluated at 750 °C for 10 h followed the order: Ni–2La–SiO₂ > Ni–4La–SiO₂ > Ni–1La–SiO₂ ≈ Ni–6La–SiO₂ > Ni–SiO₂. Ni–2La–SiO₂ catalyst possessed the lowest deactivation behavior, whose CH₄ conversion dropped from 60.2 to 55.9% after 30 h operation at 750 °C, indicating its high resistance against carbon deposition and sintering.     

助剂对顺酐加氢制备γ-丁内酯催化剂页硅酸镍性能的影响

采用蒸氨法制备含Mo、Ce、Zn助剂的页硅酸镍催化剂,考察助剂对催化剂催化顺酐加氢制备γ-丁内酯的影响。结合N₂吸附-脱附、XRD、H₂-TPR、NH₃-TPD、TEM 、XPS等表征和活性评价对催化剂的织构性质及其催化性能进行研究。结果表明,不同性质的助剂对催化剂结构及其催化性能具有显著影响。助剂Mo的掺杂,提高催化剂中镍物种的还原,增加催化剂表面金属Ni⁰的数目,在金属和酸性位协同催化下,促进催化剂催化顺酐C≡O基加氢的能力,在反应温度160 ℃、氢气压力5 MPa、反应时间180 min条件下,γ-丁内酯产率可达21.3%,是未掺杂催化剂催化活性的1.5倍。助剂Zn和Ce的加入,降低催化剂酸性,进而降低其催化活性。     

Self-sacrificial templating synthesis of flower-like nickel phyllosilicates and its application as high-performance reinforcements in epoxy nanocomposites

The nanocomposites of flower-like nickel phyllosilicate particles incorporated into epoxy resin were fabricated via an in-situ mixing process. The flower-like nickel phyllosilicate particles were firstly synthesized using a mild self-sacrificial templating method, and the morphology and lamellar structure were examined carefully. Several properties of mechanical, thermal and tribological responses of epoxy nanocomposites were performed. It was demonstrated that adequate flower-like nickel phyllosilicate particles dispersed well in the matrix, and the nanocomposites displayed enhanced tensile strength and elastic modulus but decreased elongation at break as expected. In addition, friction coefficient and wear rate were increased first and then decreased along with the particle content, and showed the lowest values at a mass fraction of 5%. Nevertheless, the incorporated flower-like nickel phyllosilicate particles resulted in the continuously increasing thermal stability of epoxy resin (EP) nanocomposites. This study revealed the giant potential of flower-like particles in preparing high-quality EP nanocomposites.     

SiO2网络限域CuO纳米晶的甲醛乙炔化性能研究

甲醛与乙炔缩合制取1,4-丁炔二醇是乙炔化工的重要方向。探讨铜基催化剂在甲醛乙炔化反应中的演变及催化作用机制,并开发更高效的甲醛乙炔化催化剂是一个值得科学与产业界关注的课题。本工作在前期页硅酸铜催化剂制备及甲醛乙炔化性能研究基础上,进一步通过热处理温度的调整,在焙烧温度为650℃时,构筑了限域于SiO₂网络结构中的CuO纳米晶催化剂。CuO纳米晶适宜的化学环境,使其在甲醛乙炔化反应初始阶段快速形成活性炔化亚铜,获得了1,4-丁炔二醇收率80%左右的结果,克服了页硅酸铜物种转化为炔化亚铜速率慢、诱导期长的弊端。SiO₂网络结构的限域作用也进一步抑制了活性组分的流失,在6次套用实验中1,4-丁炔二醇收率几乎不变,呈现出良好的使用稳定性。     

草酸二甲酯加氢催化剂Cu/SiO2的制备研究

分别用尿素和氨水为沉淀剂,采用沉淀沉积法制备了Cu/SiO2,所制催化剂均具有较高的草酸二甲酯加氢制乙二醇的活性和选择性,其中尿素均匀沉淀法更为稳定,且具有更高的选择性。同时,考察了尿素法沉淀时间、铜载量以及沉淀温度对催化剂活性的影响,并运用FTIR、BET、XRD等对催化剂进行了结构表征,活性考评及分析表征表明:沉淀时间达24 h以上,铜载量为30%,更高沉淀温度均对催化剂活性有利,催化剂具有类硅孔雀石的结构。