INFLUENCE OF THE SIZE EFFECT ON THE REGULARITIES OF THE STRUCTURE FORMATION IN BIMETALLIC Au-Co NANOPARTICLES

В данной работе методом молекулярной динамики с использованием потенциала сильной связи исследовались биметаллические наночастицы Au - Co трёх стехиометрических составов различного размера. Установлены закономерности структурообразования, описаны их характерные особенности. В частности, в составах с 50ат.% и 75ат.% содержанием Au образуются множественные малые ядра локальной икосаэдрической симметрии. Только в составе Co -25ат.% Au с увеличением размера частиц преобладают кристаллические фазы. Выявлены составы, в которых внутренняя симметрия наночастицы определена наличием одного икосаэдра, либо сверхструктуры из нескольких икосаэдров. Рассчитаны концентрационные зависимости энергии смешения биметаллической наночастицы Au - Co. Показано, что в определённом диапазоне размеров существуют концентрационные составы, при которых биметаллический наносплав может проявлять нестабильность. С использованием калорических кривых потенциальной части внутренней энергии определены температуры кристаллизации. Установлено, что температура кристаллизации демонстрирует умеренный, либо существенный, в зависимости от состава, рост с увеличением размера биметаллических наночастиц Au - Co. This work studied bimetallic Au - Co nanoparticles of three stoichiometric compositions of various sizes by the molecular dynamics method using the tight-binding potential. The regularities of structure formation are established, their characteristic features are described. In particular, in compositions with 50at% and 75at% Au content, multiple small nuclei of local icosahedral symmetry are formed. Crystalline phases prevail only in the Co - 25 at% Au composition with an increase in the particle size. Compositions are revealed in which the internal symmetry of a nanoparticle is determined by the presence of one icosahedron or a superstructure of several icosahedrons. The concentration dependences of the mixing energy of a bimetallic Au - Co nanoparticle are calculated. It is shown that there are concentrations of compositions at which bimetallic nanoalloys can exhibit instability in a certain size range. Crystallization temperatures were determined using the caloric curves of the potential part of the internal energy. It was found that the crystallization temperature demonstrates a moderate or significant, depending on the composition as well as growth with an increase in the size of bimetallic Au - Co nanoparticles.

Co/Ba/La2O3 catalyst for ammonia synthesis under mild reaction conditions

Ruthenium catalysts may allow realization of renewable energy–based ammonia synthesis processes using mild reaction conditions (<400 °C, <10 MPa). However, ruthenium is relatively rare and therefore expensive. Here, we report a Co nanoparticle catalyst loaded on a basic Ba/La2O3 support and pre-reduced at 700 °C (Co/Ba/La2O3_700red) that showed higher ammonia synthesis activity at 350 °C and 1.0–3.0 MPa than two benchmark Ru catalysts, Cs+/Ru/MgO and Ru/CeO2. The synthesis rate of the catalyst at 350 °C and 1.0 MPa (19.3 mmol h−1g−1) was 8.0 times that of Co/Ba/La2O3_500red and 6.9 times that of Co/La2O3_700red. The catalyst showed activity at temperatures down to 200 °C. High-temperature reduction induced formation of a BaO-La2O3 nano-fraction around the Co nanoparticles, which increased turnover frequency, inhibited Co nanoparticle sintering, and suppressed ammonia poisoning. These strategies may also be appliable to nickel catalysts.

Catalytic Hydrogen Evolution of NaBH4 Hydrolysis by Cobalt Nanoparticles Supported on Bagasse-Derived Porous Carbon

As a promising hydrogen storage material, sodium borohydride (NaBH4) exhibits superior stability in alkaline solutions and delivers 10.8 wt.% theoretical hydrogen storage capacity. Nevertheless, its hydrolysis reaction at room temperature must be activated and accelerated by adding an effective catalyst. In this study, we synthesize Co nanoparticles supported on bagasse-derived porous carbon (Co@xPC) for catalytic hydrolytic dehydrogenation of NaBH4. According to the experimental results, Co nanoparticles with uniform particle size and high dispersion are successfully supported on porous carbon to achieve a Co@150PC catalyst. It exhibits particularly high activity of hydrogen generation with the optimal hydrogen production rate of 11086.4 mLH2∙min−1∙gCo−1 and low activation energy (Ea) of 31.25 kJ mol−1. The calculation results based on density functional theory (DFT) indicate that the Co@xPC structure is conducive to the dissociation of [BH4]−, which effectively enhances the hydrolysis efficiency of NaBH4. Moreover, Co@150PC presents an excellent durability, retaining 72.0% of the initial catalyst activity after 15 cycling tests. Moreover, we also explored the degradation mechanism of catalyst performance.

Antibacterial Films of Alginate-CoNi-Coated Cellulose Paper Stabilized Co NPs for Dyes and Nitrophenol Degradation

The development of a solid substrate for the support and stabilization of zero-valent metal nanoparticles (NPs) is the heart of the catalyst system. In the current embodiment, we have prepared solid support comprise of alginate-coated cellulose filter paper (Alg/FP) for the synthesis and stabilization of Co nanoparticles (NPs) named as Alg/FP@Co NPs. Furthermore, Alginate polymer was blended with 1 and 2 weight percent of CoNi NPs to make Alg-CoNi1/FP and Alg-CoNi2/FP, respectively. All these stabilizing matrixes were used as dip-catalyst for the degradation of azo dyes and reduction of 4-nitrophenol (4NP). The effect of initial dye concentration, amount of NaBH4, and catalyst dosage was assessed for the degradation of Congo red (CR) dye by using Alg-CoNi2/FP@Co NPs. Results indicated that the highest kapp value (3.63 × 10−1 min−1) was exhibited by Alg-CoNi2/FP@Co NPs and lowest by Alg/FP@Co NPs against the discoloration of CR dye. Furthermore, it was concluded that Alg-CoNi2/FP@Co NPs exhibited strong catalyst activity against CR, and methyl orange dye (MO) degradation as well as 4NP reduction. Antibacterial activity of the prepared composites was also investigated and the highest l activity was shown by Alg-CoNi2/FP@Co NPs, which inhibit 2.5 cm zone of bacteria compared to other catalysts.