Reduced metal nanocatalysts for selective electrochemical hydrogenation of biomass-derived 5-(hydroxymethyl)furfural to 2,5-bis(hydroxymethyl)furan in ambient conditions.

Selective electrochemical hydrogenation (ECH) of biomass-derived unsaturated organic molecules has enormous potential for sustainable chemical production. However, an efficient catalyst is essential to perform an ECH reaction consisting of superior product selectivity and a higher conversion rate. Here, we examined the ECH performance of reduced metal nanostructures, i.e., reduced Ag (rAg) and reduced copper (rCu) prepared via electrochemical or thermal oxidation and electrochemical reduction process, respectively. Surface morphological analysis suggests the formation of nanocoral and entangled nanowire structure formation for rAg and rCu catalysts. rCu exhibits a slight enhancement in ECH reaction performance in comparison to the pristine Cu. However, the rAg exhibits more than two times higher ECH performance without compromising the selectivity for 5-(HydroxyMethyl) Furfural (HMF) to 2,5-bis(HydroxyMethyl)-Furan (BHMF) formation in comparison to the Ag film. Moreover, a similar ECH current density was recorded at a reduced working potential of 220 mV for rAg. This high performance of rAg is attributed to the formation of new catalytically active sites during the Ag oxidation and reduction processes. This study demonstrates that rAg can potentially be used for the ECH process with minimum energy consumption and a higher production rate.

Comparative investigation of gas sensing performance of liquefied petroleum gas using green reduced graphene oxide-based sensors.

Herein, we report the comparative gas sensing performance (at room temperature) of reduced graphene oxide sensors obtained by reducing graphene oxide using extracts of pumpkin leaf, neem leaf and methionine. An interdigitated pattern was designed on soda-lime glass using a stamp method and the dispersed solution of rGO was spin coated on the pattern. The electrical response of the sensors was investigated (using a simple in-house measurement set up) by measuring change in resistance of graphene with varying gas concentration on exposure to liquefied petroleum gas (LPG). From the characterization results using FTIR, SEM, EDX and UV-Visible, methionine reduced graphene oxide (MRGO 12H) indicated a greater degree of reduction compared to pumpkin reduced graphene oxide (PRGO 12H) and neem reduced graphene oxide (NRGO 12H). The LPG sensing results showed an increase in the resistance of the sensor materials upon the introduction of the gas and, an increased sensitivity as the concentration of the test gas increased from 100 ppm to 200 ppm while the MRGO 12H sensor was more selective towards LPG sensing. Furthermore, it was observed that the sensor response for the fabricated sensors is strongly dependent on the concentration of gas exposed to the sensors and the degree of removal of oxygen functional groups in the graphene-based materials. Hence, the MRGO 12H sensor had a sensor response of 23.58% at 200 ppm. PRGO 12H at 100 ppm illustrates the least sensor response while NRGO 12H showed very poor sensor response that ranged between 5.10% and 7.56%. The sensor response of the materials demonstrates an improvement in results obtained for pure rGO based sensors. We obtained a response time as low as 5.3 seconds for MRGO 12H while the recovery time of the sensors ranged between 6.46 seconds and 41.50 seconds. The MRGO 12H sensor typified the best recovery time and thus outperformed results from most of the reported literature. Considering different performance metrics such as sensor response, response time, recovery time and sensing period, MRGO 12H is more selective towards detecting LPG. Our results showed that a greater restoration of the sp2 carbon chain brought about by increased reduction of graphene oxide is largely responsible for the sensing behavior of rGO towards LPG.

Low Platinum-Loaded Molybdenum Co-catalyst for the Hydrogen Evolution Reaction in Alkaline and Acidic Media.

Developing an efficient catalytic system for electrolysis with reduced platinum (Pt) loading while maintaining performance comparable to bulk platinum metal is important to decrease costs and improve scalability of the hydrogen fuel economy. Here we report the performance of a novel sputter-deposited molybdenum (Mo) thin film with an extremely low co-loading of Pt, where Pt atoms were dispersed on Mo (Ptd-Mo) as an electrocatalyst for the hydrogen evolution reaction (HER) in either alkaline or acidic media. The Ptd-Mo electrocatalyst presents similar catalytic activity to bulk Pt in alkaline media, while the performance is only slightly decreased in acidic media. Differential electrochemical mass spectrometry (DEMS) results confirm that the Ptd-Mo electrocatalyst produced hydrogen at a rate comparable with that of a pristine Pt sample at the same potential. A comparison with Pt-loaded degenerately doped p-type doped silicon (Ptd-Si) suggests that Mo and Pt work synergistically to boost the performance of Ptd-Mo catalysts. Cyclic voltammetry (CV) and X-ray photoelectron spectroscopy (XPS) before and after 1000 cycles of continuous operation confirm the significant durability of the Ptd-Mo performance. Overall, the Ptd-Mo electrocatalyst, with comparable HER activity to bulk Pt despite an ultra-low Pt loading, could be a strong candidate for hydrogen production in either acidic or basic conditions.

Cu and Ni Co-sputtered heteroatomic thin film for enhanced nonenzymatic glucose detection.

In this work, we report a wafer-scale and chemical-free fabrication of nickel (Ni) and copper (Cu) heteroatomic Cu-Ni thin films using RF magnetron sputtering technique for non-enzymatic glucose sensing application. The as-prepared wafer-scale Cu-Ni thin films exhibits excellent electrocatalytic activity toward glucose oxidation with a 1.86 µM detection limit in the range of 0.01 mM to 20 mM range. The Cu-Ni film shows 1.3- and 5.4-times higher glucose oxidation activity in comparison to the Cu and Ni electrodes, respectively. The improved electrocatalytic activity is attributed to the synergistic effect of the bimetallic catalyst and high density of grain boundaries. The Cu-Ni electrodes also possessed excellent anti-interference characteristics. These results indicate that Cu-Ni heteroatomic thin film can be a potential candidate for the development of non-enzymatic glucose biosensor because of its chemical free synthesis, excellent reproducibility, reusability, and long-term stability.