Ammonia Detection Methods in Photocatalytic and Electrocatalytic Experiments: How to Improve the Reliability of NH3 Production Rates?
ABSTRACT: The enzyme nitrogenase inspires the development of novel photocatalytic and electrocatalytic systems that can drive nitrogen reduction with water under similar low-temperature and low-pressure conditions. While photocatalytic and electrocatalytic N2 fixation are emerging as hot new areas of fundamental and applied research, serious concerns exist regarding the accuracy of current methods used for ammonia detection and quantification. In most studies, the ammonia yields are low and little consideration is given to the effect of interferants on NH3 quantification. As a result, NH3 yields reported in many works may be exaggerated and erroneous. Herein, the advantages and limitations of the various methods commonly used for NH3 quantification in solution (Nessler's reagent method, indophenol blue method, and ion chromatography method) are systematically explored, placing particular emphasis on the effect of interferants on each quantification method. Based on the data presented, guidelines are suggested for responsible quantification of ammonia in photocatalysis and electrocatalysis.
Project description:Bridging iron hydrides are proposed to form at the active site of MoFe-nitrogenase during catalytic dinitrogen reduction to ammonia and may be key in the binding and activation of N2 via reductive elimination of H2 . This possibility inspires the investigation of well-defined molecular iron hydrides as precursors for catalytic N2 -to-NH3 conversion. Herein, we describe the synthesis and characterization of new P2P'Ph Fe(N2 )(H)x systems that are active for catalytic N2 -to-NH3 conversion. Most interestingly, we show that the yields of ammonia can be significantly increased if the catalysis is performed in the presence of mercury lamp irradiation. Evidence is provided to suggest that photo-elimination of H2 is one means by which the enhanced activity may arise.
Project description:Electrocatalytic N2 reduction reaction (NRR) into ammonia (NH3), especially if driven by renewable energy, represents a potentially clean and sustainable strategy for replacing traditional Haber-Bosch process and dealing with climate change effect. However, electrocatalytic NRR process under ambient conditions often suffers from low Faradaic efficiency and high overpotential. Developing newly regulative methods for highly efficient NRR electrocatalysts is of great significance for NH3 synthesis. Here, we propose an interfacial engineering strategy for designing a class of strongly coupled hybrid materials as highly active electrocatalysts for catalytic N2 fixation. X-ray absorption near-edge spectroscopy (XANES) spectra confirm the successful construction of strong bridging bonds (Co-N/S-C) at the interface between CoS x nanoparticles and NS-G (nitrogen- and sulfur-doped reduced graphene). These bridging bonds can accelerate the reaction kinetics by acting as an electron transport channel, enabling electrocatalytic NRR at a low overpotential. As expected, CoS2/NS-G hybrids show superior NRR activity with a high NH3 Faradaic efficiency of 25.9% at -0.05 V versus reversible hydrogen electrode (RHE). Moreover, this strategy is general and can be extended to a series of other strongly coupled metal sulfide hybrids. This work provides an approach to design advanced materials for ammonia production.
Project description:Ammonium bicarbonate (NH4HCO3) was generated by the absorption of carbon dioxide (CO2) into an aqueous solution of ammonia (NH3). NH4HCO3 was successfully used to achieve highly efficient photocatalytic conversion of CO2 to carbon monoxide (CO). NH3 and/or ammonium ions (NH4+) derived from NH4HCO3 in aqueous solution were decomposed into nitrogen (N2) and hydrogen (H2). Stoichiometric amounts of the N2 oxidation product and the CO and H2 reduction products were generated when the photocatalytic reaction was carried out in aqueous NH4HCO3 solution. NH3 and/or NH4+ functioned as electron donors in the photocatalytic conversion of CO2 to CO. A CO formation rate of 0.5 mmol h-1 was obtained using 500 mg of catalyst (approximately 7500 ppm) in ambient conditions (303 K, 101.3 kPa). Our results demonstrated that NH4HCO3 is a novel inorganic sacrificial reagent, which can be used to increase the efficiency of photocatalytic CO production to achieve one step CO2 capture, storage and conversion.
Project description:Quantification of ammonia in whole blood has applications in the diagnosis and management of many hepatic diseases, including cirrhosis and rare urea cycle disorders, amounting to more than 5 million patients in the United States. Current techniques for ammonia measurement suffer from limited range, poor resolution, false positives or large, complex sensor set-ups. Here we demonstrate a technique utilizing inexpensive reagents and simple methods for quantifying ammonia in 100 ?L of whole blood. The sensor comprises a modified form of the indophenol reaction, which resists sources of destructive interference in blood, in conjunction with a cation-exchange membrane. The presented sensing scheme is selective against other amine containing molecules such as amino acids and has a shelf life of at least 50 days. Additionally, the resulting system has high sensitivity and allows for the accurate reliable quantification of ammonia in whole human blood samples at a minimum range of 25 to 500 ?M, which is clinically for rare hyperammonemic disorders and liver disease. Furthermore, concentrations of 50 and 100 ?M ammonia could be reliably discerned with p = 0.0001.
Project description:Adenosine is a major local regulator of tissue function and industrially useful as precursor for the production of medicinal nucleoside substances. High-throughput screening of adenosine overproducers is important for industrial microorganism breeding. An enzymatic assay of adenosine was developed by combined adenosine deaminase (ADA) with indophenol method. The ADA catalyzes the cleavage of adenosine to inosine and NH3 , the latter can be accurately determined by indophenol method. The assay system was optimized to deliver a good performance and could tolerate the addition of inorganic salts and many nutrition components to the assay mixtures. Adenosine could be accurately determined by this assay using 96-well microplates. Spike and recovery tests showed that this assay can accurately and reproducibly determine increases in adenosine in fermentation broth without any pretreatment to remove proteins and potentially interfering low-molecular-weight molecules. This assay was also applied to high-throughput screening for high adenosine-producing strains. The high selectivity and accuracy of the ADA assay provides rapid and high-throughput analysis of adenosine in large numbers of samples.
Project description:Ammonia (NH3) production from electrochemical nitrogen (N2) reduction reaction (NRR) under ambient conditions represents a sustainable alternative to the traditional Haber-Bosch process. However, the conventional electrocatalytic NRR process often suffers from low selectivity (competition with the hydrogen evolution reaction (HER)) and electron transfer bottleneck for efficient activation and dissociation. Herein, a strategy to simultaneously promote selectivity and activity through dual-incorporation of Se and O elements onto the shell of HER-inactive Te nanorods is reported. It is theoretically and experimentally verified that the exposure of lone-pair electrons in the TeO2 shell of Se, O dual-doped Te nanorods can maximize orbits overlap between N2 and Te for N-N bond activation via ?-backdonation interactions. Further, the Gibbs free energy change indicates that the Lewis-basic anchor -SeO ligand with strong electron-donating characteristics serves as an electron reservoir and is capable of buffering the oxidation state variation of Te, thereby improving the thermodynamics of desorption of the intermediates in the N2-to-NH3 conversion process. As expected, a high faradaic efficiency of 24.56% and NH3 yield rate of ?21.54 µg h-1 mg-1 are obtained under a low overpotential of ?0.30 V versus reversible hydrogen electrode in an aqueous electrolyte under ambient conditions.
Project description:Cytidine is an industrially useful precursor for the production of antiviral compounds and a variety of industrial compounds. Interest in the microbial production of cytidine has grown recently and high-throughput screening of cytidine over-producers is an important approach in large-scale industrial production using microorganisms. An enzymatic assay for cytidine was developed combining cytidine deaminase (CDA) and indophenol method. CDA catalyzes the cleavage of cytidine to uridine and NH3, the latter of which can be accurately determined using the indophenol method. The assay was performed in 96-well plates and had a linear detection range of cytidine of 0.058-10 mM. This assay was used to determine the amount of cytidine in fermentation flasks and the results were compared with that of High Perfomance Liquid Chromatography (HPLC) method. The detection range of the CDA method is not as wide as that of the HPLC, furthermore the correlation factor of CDA method is not as high as that of HPLC. However, it was suitable for the detection of large numbers of crude samples and was applied to high-throughput screening for high cytidine-producing strains using 96-well deep-hole culture plates. This assay was proved to be simple, accurate, specific and suitable for cytidine detection and high-throughput screening of cytidine-producing strains in large numbers of samples (96 well or more).
Project description:Ammonia (NH3) is one of the most widely produced chemicals worldwide. It has application in the production of many important chemicals, particularly fertilizers. It is also, potentially, an important energy storage intermediate and clean energy carrier. Ammonia production, however, mostly uses fossil fuels and currently accounts for more than 1.6% of global CO2 emissions (0.57 ?Gt in 2015). Here we describe a solar-driven nanostructured photoelectrochemical cell based on plasmon-enhanced black silicon for the conversion of atmospheric N2 to ammonia producing yields of 13.3?mg?m(-2)?h(-1) under 2 suns illumination. The yield increases with pressure; the highest observed in this work was 60?mg?m(-2)?h(-1) at 7?atm. In the presence of sulfite as a reactant, the process also offers a direct solar energy route to ammonium sulfate, a fertilizer of economic importance. Although the yields are currently not sufficient for practical application, there is much scope for improvement in the active materials in this cell.
Project description:In open beef feedlot systems, more than 50% of dietary nitrogen (N) is lost as ammonia (NH3). Here we report an effective and economically-viable method to mitigate NH3 emissions by the application of lignite. We constructed two cattle pens (20 × 20 m) to determine the effectiveness of lignite in reducing NH3 emissions. Twenty-four steers were fed identical commercial rations in each pen. The treatment pen surface was dressed with 4.5 kg m(-2) lignite dry mass while no lignite was applied in the control pen. We measured volatilised NH3 concentrations using Ecotech EC9842 NH3 analysers in conjunction with a mass balance method to calculate NH3 fluxes. Application of lignite decreased NH3 loss from the pen by approximately 66%. The cumulative NH3 losses were 6.26 and 2.13 kg N head(-1) in the control and lignite treatment, respectively. In addition to the environmental benefits of reduced NH3 losses, the value of retained N nutrient in the lignite treated manure is more than $37 AUD head(-1) yr(-1), based on the current fertiliser cost and estimated cost of lignite application. We show that lignite application is a cost-effective method to reduce NH3 loss from cattle feedlots.
Project description:Klebsiella pneumoniae nitrogenase reduced azide, at 30 degrees C and pH 6.8-8.2, to yield ammonia (NH3), dinitrogen (N2) and hydrazine (N2H4). Reduction of (15N = 14N = 14N)-followed by mass-spectrometric analysis showed that no new nitrogen-nitrogen bonds were formed. During azide reduction, added 15N2H4 did not contribute 15N to NH3, indicating lack of equilibration between enzyme-bound intermediates giving rise to N2H4 and N2H4 in solution. When azide reduction to N2H4 was partially inhibited by 15N2, label appeared in NH3 but not in N2H4. Product balances combined with the labelling data indicate that azide is reduced according to the following equations: (formula: see text); N2 was a competitive inhibitor and CO a non-competitive inhibitor of azide reduction to N2H4. The percentage of total electron flux used for H2 evolution concomitant with azide reduction fell from 26% at pH 6.8 to 0% at pH 8.2. Pre-steady-state kinetic data suggest that N2H4 is formed by the cleavage of the alpha-beta nitrogen-nitrogen bond to bound azide to leave a nitride (= N) intermediate that subsequently yields NH3.