Tandem electrocatalytic N2 fixation via concerted proton-electron transfer

New electrochemical ammonia (NH3) synthesis technologies are of interest as a complementary route to the Haber-Bosch (HB) process for distributed fertilizer generation, and towards exploiting ammonia as a zero-carbon fuel produced via renewably-sourced electricity.1–4 Apropos of these goals is a surge of fundamental research targeting heterogeneous materials5–7 as electrocatalysts for the nitrogen reduction reaction (N2RR). These systems generally suffer from poor stability and NH3 selectivity; competitive hydrogen evolution reaction (HER) outcompetes N2RR.8 Molecular catalyst systems can be exquisitely tuned and offer an alternative strategy,9 but progress has thus far been thwarted by the same selectivity issue; HER dominates. Herein we describe a tandem catalysis strategy that offers a solution to this puzzle. A molecular complex that can mediate an N2 reduction cycle is partnered with a co-catalyst that interfaces the electrode and an acid to mediate concerted proton-electron transfer (CPET) steps, facilitating N−H bond formation at a favorable applied potential and overall thermodynamic efficiency. Without CPET, certain intermediates of the N2RR cycle would be unreactive via independent electron transfer (ET) or proton transfer (PT) steps, thereby shunting the system. Promisingly, complexes featuring several metals (W, Mo, Os, Fe) achieve N2RR electrocatalysis at the same applied potential in the presence of the CPET mediator, pointing to the generality of this tandem approach.

Tandem electrocatalytic N2 fixation via concerted proton-electron transfer

New electrochemical ammonia (NH3) synthesis technologies are of interest as a complementary route to the Haber-Bosch (HB) process for distributed fertilizer generation, and towards exploiting ammonia as a zero-carbon fuel produced via renewably-sourced electricity. Apropos of these goals is a surge of fundamental research targeting heterogeneous materials as electrocatalysts for the nitrogen reduction reaction (N2RR). These systems generally suffer from poor stability and NH3 selectivity; competitive hydrogen evolution reaction (HER) outcompetes N2RR. Molecular catalyst systems can be exquisitely tuned and offer an alternative strategy, but progress has thus far been thwarted by the same selectivity issue; HER dominates. Herein we describe a tandem catalysis strategy that offers a solution to this puzzle. A molecular complex that can mediate an N2 reduction cycle is partnered with a co-catalyst that interfaces the electrode and an acid to mediate concerted proton-electron transfer (CPET) steps, facilitating N−H bond formation at a favorable applied potential and overall thermodynamic efficiency. Without CPET, certain intermediates of the N2RR cycle would be unreactive via independent electron transfer (ET) or proton transfer (PT) steps, thereby shunting the system. Promisingly, complexes featuring several metals (W, Mo, Os, Fe) achieve N2RR electrocatalysis at the same applied potential in the presence of the CPET mediator, pointing to the generality of this tandem approach.

The formation of methanol from glycerol bio-waste over doped ceria-based catalysts

A series of ceria-based solid solution metal oxides were prepared by co-precipitation and evaluated as catalysts for glycerol cleavage, principally to methanol. The catalyst activity and selectivity to methanol were investigated with respect to the reducibility of the catalysts. Oxides comprising Ce-Pr and Ce-Zr were prepared, calcined and compared to CeO 2 , Pr 6 O 11 and ZrO 2 . The oxygen storage capacity of the catalysts was examined with analysis of Raman spectroscopic measurements and a temperature programmed reduction, oxidation and reduction cycle. The incorporation of Pr resulted in significant defects, as evidenced by Raman spectroscopy. The materials were evaluated as catalysts for the glycerol to methanol reaction, and it was found that an increased defect density or reducibility was beneficial. The space–time yield of methanol normalized to surface area over CeO 2 was found to be 0.052 mmol MeOH m −2 h −1 , and over CeZrO 2 and CePrO 2 , this was to 0.029 and 0.076 mmol MeOH m −2 h −1 , respectively. The inclusion of Pr reduced the surface area; however, the carbon mole selectivity to methanol and ethylene glycol remained relatively high, suggesting a shift in the reaction pathway compared to that over ceria. This article is part of a discussion meeting issue ‘Science to enable the circular economy'.

A Label-Free Electrochemical Immunosensor for Detection of the Tumor Marker CA242 Based on Reduced Graphene Oxide-Gold-Palladium Nanocomposite

As a tumor marker, carbohydrate antigen 24-2 (CA242) is a highly accurate and specific diagnostic indicator for monitoring pancreatic and colorectal cancers. The goal of this study was to create a novel label-free electrochemical immunosensor using a nanocomposite glassy carbon electrode for the detection of CA242. Graphene oxide (GO) and polyvinyl pyrrolidone were chosen as the dopants for the preparation of a high-performance reduced-GO-gold-palladium (rGO-Au-Pd) nanocomposite. RGO-Au-Pd was characterized using X-ray diffraction and transmission electron microscopy, revealing that the material exhibited superior electrochemical redox activity and electron transfer ability. The effects of the synthesis method, material concentration, reduction cycle, and pH were investigated to optimize the performance of the immunosensor. As a result of the catalytic activity and biocompatibility of rGO-Au-Pd, the prepared CA242 immunosensor displayed a wide linear range of detection from 0.001 U/mL to 10,000 U/mL with a detection limit of 1.54 × 10−3 U/mL and a sensitivity of 4.24 μA (log10CCA242)−1. More importantly, the immunosensor exhibited satisfactory reproducibility and selectivity when detected CA242 in PBS or human serum. The results of our study provide a platform for the development of novel bioassays for use in early cancer diagnosis and promote the application of biosensing technology in the medical field.

New Manufacturing Takes Flight

Pratt & Whitney’s Industry 4.0 initiative marks a major transformation from the labor-intensive manual processes that once defined manufacturing to those that are now digitized and automated. The changes here helped P&W improve key metrics—production volume, quality assurance, labor reduction, cycle time, to name a few—by up to 65 percent. This article takes a closer look at how companies not only have to update the types of machines and systems they use to remain competitive, but they also have to change the way they recruit, hire, and train the engineers and technicians who work on them.

Mechanical Characterization of Reduced Graphene Oxide Using AFM

Nanoindentation coupled with Atomic Force Microscopy was used to study stiffness, hardness, and the reduced Young’s modulus of reduced graphene oxide. Oxygen reduction on the graphene oxide sample was performed via LightScribe DVD burner reduction, a cost-effective approach with potential for large scale graphene production. The reduction of oxygen in the graphene oxide sample was estimated to about 10 percent using FTIR spectroscopic analysis. Images of the various samples were captured after each reduction cycle using Atomic Force Microscopy. Elastic and spectroscopic analyses were performed on the samples after each oxygen reduction cycle in the LightScribe, thus allowing for a comparison of stiffness, hardness, and the reduced Young’s modulus based on the number of reduction cycles. The highest values obtained were after the fifth and final reduction cycle, yielding a stiffness of 22.4 N/m, a hardness of 0.55 GPa, and a reduced Young’s modulus of 1.62 GPa as compared to a stiffness of 22.8 N/m, a hardness of 0.58 GPa, and a reduced Young’s modulus of 1.84 GPa for a commercially purchased graphene film made by CVD. This data was then compared to the expected values of pristine single layer graphene. Furthermore, two RC circuits were built, one using a parallel plate capacitors made of light scribed graphene on a kapton substrate (LSGC) and a second one using a CVD deposited graphene on aluminum (CVDGC). Their RC time constants and surface charge densities were compared.

A review on CO oxidation, methanol synthesis, and propylene epoxidation over supported gold catalysts

The aim of this general review is to give an overview of the reaction pathways involving the transformation of carbon monoxide (CO), methanol synthesis and propylene epoxidation using gold (Au) and gold supported clusters. Over the catalyst system of Nano-gold (Au/SiO2), the process of methane to methanol was also highlighted. A reaction mechanism proposed, indicated that molecular oxygen was consumed in the oxidation–reduction cycle. Consequently, methane oxidation to methanol can be achieved as a green chemical process. The system can also be used in other green chemical processes of liquid phase or gas phase oxidations. Methanol is expected to be a potential solution to the partial deployment of fossil source-based economies. Moreover, it is a recognized energy carrier that is better than other alternatives in terms of transportation, storage and reuse. New or improved catalysts for methanol production are likely to be discovered in the near future.