Room Temperature Nanographene Production via CO2 Electrochemical Reduction on the Electrodeposited Bi on Sn Substrate.

Electrochemical reduction of carbon dioxide (CO2RR) to crystalline solid carbon at room temperature is challenging, but it is a providential CO2 utilization route due to its indefinite storage and potential applications of its products in many advanced technologies. Here, room-temperature synthesis of polycrystalline nanographene was achieved by CO2RR over the electrodeposited Bi on Sn substrate prepared with various bismuth concentrations (0.01 M, 0.05 M, and 0.1 M). The solid carbon products were solely produced on all the prepared electrodes at the applied potential -1.1 V vs. Ag/AgCl and were characterized as polycrystalline nanographene with an average domain size of ca. 3-4 nm. The morphology of the electrodeposited Bi/Sn electrocatalysts did not have much effect on the final structure of the solid carbon products formed but rather affected the CO2 electroreduction activity. The optimized negative potential for the formation of nanographene products on the 0.05Bi/Sn was ca. -1.5 V vs. Ag/AgCl. Increasing the negative value of the applied potential accelerated the agglomeration of the highly reactive nascent Bi clusters in situ formed under the reaction conditions, which, as a consequence, resulted in a slight deviation of the product selectivity toward gaseous CO and H2 evolution reaction. The Bi-graphene composites produced by this method show high potential as an additive for working electrode modification in electrochemical sensor-related applications.

Formation and growth characteristics of nanostructured carbon films on nascent Ag clusters during room-temperature electrochemical CO2 reduction.

Synthesis of carbon nanostructures at room temperature and under atmospheric pressure is challenging but it can provide significant impact on the development of many future advanced technologies. Here, the formation and growth characteristics of nanostructured carbon films on nascent Ag clusters during room-temperature electrochemical CO2 reduction reactions (CO2RR) are demonstrated. Under a ternary electrolyte system containing [BMIm]+[BF4]-, propylene carbonate, and water, a mixture of sp2/sp3 carbon allotropes were grown on the facets of Ag nanocrystals as building blocks. We show that (i) upon sufficient energy supplied by an electric field, (ii) the presence of negatively charged nascent Ag clusters, and (iii) as a function of how far the C-C coupling reaction of CO2RR (10-390 min) has advanced, the growth of nanostructured carbon can be divided into three stages: Stage 1: sp3-rich carbon and diamond seed formation; stage 2: diamond growth and diamond-graphite transformation; and stage 3: amorphous carbon formation. The conversion of CO2 and high selectivity for the solid carbon products (>95%) were maintained during the full CO2RR reaction length of 390 min. The results enable further design of the room-temperature production of nanostructured carbon allotropes and/or the corresponding metal-composites by a viable negative CO2 emission technology.

Optimal Conditions for Butanol Production from Ethanol over MgAlO Catalyst Derived from Mg-Al Layer Double Hydroxides.

The MgAlO catalyst was obtained from thermal decomposition of the MgAl-LDH catalyst having Mg/Al molar ratio of 5. The catalytic Guerbet reaction of ethanol was investigated to determine the effect of WHSV and nitrogen flow rate on butanol production and product distribution. It was performed in a fixed-bed microreactor under continuous flow of vaporized ethanol mixed with N2. The MgAlO catalyst had high total basic sites and high total acid sites that were crucial for ethanol Guerbet reaction. The MgAlO catalyst showed the highest butanol selectivity at 300℃ under WHSV = 3.10 h-1 and nitrogen flow rate = 3,600 mL/h, and the highest butanol yield at 400℃ under WHSV = 3.10 h-1 and nitrogen flow rate = 900 mL/h. It can be summarized that in order to enhance the butanol yield, the low WHSV is preferred to increase the contact time of ethanol and catalyst under moderate temperature.

Effect of the Nanostructured Zn/Cu Electrocatalyst Morphology on the Electrochemical Reduction of CO2 to Value-Added Chemicals.

Zn/Cu electrocatalysts were synthesized by the electrodeposition method with various bath compositions and deposition times. X-ray diffraction results confirmed the presence of (101) and (002) lattice structures for all the deposited Zn nanoparticles. However, a bulky (hexagonal) structure with particle size in the range of 1-10 µm was obtained from a high-Zn-concentration bath, whereas a fern-like dendritic structure was produced using a low Zn concentration. A larger particle size of Zn dendrites could also be obtained when Cu2+ ions were added to the high-Zn-concentration bath. The catalysts were tested in the electrochemical reduction of CO2 (CO2RR) using an H-cell type reactor under ambient conditions. Despite the different sizes/shapes, the CO2RR products obtained on the nanostructured Zn catalysts depended largely on their morphologies. All the dendritic structures led to high CO production rates, while the bulky Zn structure produced formate as the major product, with limited amounts of gaseous CO and H2. The highest CO/H2 production rate ratio of 4.7 and a stable CO production rate of 3.55 µmol/min were obtained over the dendritic structure of the Zn/Cu-Na200 catalyst at -1.6 V vs. Ag/AgCl during 4 h CO2RR. The dissolution and re-deposition of Zn nanoparticles occurred but did not affect the activity and selectivity in the CO2RR of the electrodeposited Zn catalysts. The present results show the possibilities to enhance the activity and to control the selectivity of CO2RR products on nanostructured Zn catalysts.

Oxidative Dehydrogenation of Ethanol over Vanadium- and Molybdenum-modified Mg-Al Mixed Oxide Derived from Hydrotalcite.

Hydrotalcite or Mg-Al LDHs were synthesized by co-precipitation method. The Mg-Al mixed oxide was then derived by calcination of hydrotalcite at 450°C. The metal modified catalysts (Mo/Mg-Al and V/Mg-Al) were prepared by incipient wetness impregnation method. The obtained catalysts were characterized by several useful techniques and tested the reactivity for dehydrogenation and oxidative dehydrogenation of ethanol (gas-phase) to produce acetaldehyde. The catalytic reactions were performed at temperature range from 200 to 400°C for both non-oxidative and oxidative atmospheres. The results showed that the vanadium-modified hydrotalcite (V/Mg-Al) exhibited the highest ethanol conversion (34.3%) and acetaldehyde yield (15.5%) at 400℃ in the non-oxidative atmosphere. For the oxidative dehydrogenation of ethanol, the V/Mg-Al catalyst showed the highest activity at 400°C giving the ethanol conversion and acetaldehyde yield of 73.7% and 29.5%, respectively. This result probably related to the highest base density of V/Mg-Al catalyst (6.13 µmol CO2/m2) measured by CO2-TPD. The catalytic activity of Mg-Al catalyst and metal modified catalyst slightly decreased upon time-on-stream test for 10 h on oxidative dehydrogenation of ethanol due to carbon deposition.

Effect of Calcination Temperature on Mg-Al Layered Double Hydroxides (LDH) as Promising Catalysts in Oxidative Dehydrogenation of Ethanol to Acetaldehyde.

Oxidative dehydrogenation of ethanol to acetaldehyde over Mg-Al layered double hydroxides (LDH) and their differently calcined derivative catalysts was investigated in this study. The Mg-Al catalysts were synthesized via co-precipitation method and calcined at different temperatures at 450°C, 600°C and 900°C. It revealed that the calcination temperature affected the physicochemical properties and the catalytic activity of these catalysts toward the oxidative dehydrogenation of ethanol. It was found that ethanol conversion increased with increasing reaction temperature from 200 to 400°C, whereas acetaldehyde selectivity decreased. At low reaction temperature (200-300°C), the non-calcined catalyst (Mg-Al-000) showed the highest ethanol conversion, which can be attributed to the hydroxyl groups on surface having acetaldehyde as a major product. The calcination process led to formation of mixed oxide phase in Mg-Al catalysts as proven by the XRD and FT-IR results. The catalyst calcined at 450°C (Mg-Al-450) exhibited the highest basicity as measured by the CO2-TPD with ethanol conversion of 45.8% and acetaldehyde yield of 29.7% at 350°C.