Plasma assisted electrocatalytic conversion

Abstract

A method of reducing a gaseous compound, for example, nitrogen or carbon dioxide, the method comprising the steps of subjecting the gaseous compound to plasma forming conditions to form a plasma; contacting the plasma with water or an electrolyte at a plasma-water or electrolyte-water interface, thereby to provide a dissolved plasma derived species; and electrocatalytically reducing said dissolved plasma derived species to provide a reduced compound. The plasma may for example be generated by a combination of glow discharge and spark discharge in a configuration of a pin-to-liquid with no enclosure, pin-to-liquid with nozzle enclosure, or a pin-to-liquid with a column bubbler enclosure. A catalyst, such as transition metal, maybe added, advantageously in the form of a nano structured catalyst.

Description

The present invention relates to a new, hybrid technology for the production of a reduced gaseous species (such as ammonia) via clean and renewable sources. The technology is based on the coupling between two fundamental aspects: plasma-assisted activation of gas; and electrocatalytic conversation of relevant plasma species to the reduced gaseous species. Gaseous species, for example, ground-state nitrogen molecules, exhibit high ionization potential. This is intrinsically non-reactive for thermodynamic standpoint, but plasma activation can provide avenues for the conversion of highly stable nitrogen molecules into easier-to-breakdown species. These species can then be more efficiently converted into ammonia electrochemically. The hybrid system of the present invention can operate under ambient conditions, with water and air being reactants. Further, the ammonia produced is in aqueous phase, thus requiring no further pre-treatment stages for application areas such as direct use as fertilizer and in the textile and explosives industries. The present invention is a hybrid plasma-electrocatalytic system which activates an input feed gas to form a plasma at the liquid / gas interface of the reactant gas within the liquid (typically water / electrolyte). The resulting activated species are dissolved in the liquid, and subsequently converted into valuable chemicals by means of electrocatalysis. The invention relates to the method, apparatus and also to specific features of the system, in particular features such as the catalyst design. This present invention can be used to convert a variety of reducible gases into reduced species but in general, it will be discussed herein with reference to the conversion of nitrogen (either as supplied nitrogen or air) and water to ammonia. In this process nitrogen is bubbled into the liquid (water or electrolyte) while being subjected to an atmospheric pressure plasma discharge, enabling the transport of the activated species within the liquid. These species (particularly nitrates and nitrites) can be then efficiently converted into ammonia by using a designed electrocatalyst. In addition to the reduction of nitrogen, it should be noted that the process can be advantageously used in electrocatalytic carbon dioxide reduction reaction, which requires transformation of stable carbon dioxide molecules into comparatively more energetic and reactive states, which this invention can provide thus delivering enhanced performance as well as controllable selectivity. A particular advantage of the present invention may be found where in reactions where the gas phase activation is the rate determining step. As aforementioned, two of the most significant inhibitors to electrocatalytic NRR (eNRR) are the high stability and low solubility of the N2 molecule in liquids. The present invention seeks to overcome these limitations by converting N2 into a more reactive and soluble form. Nitrate and nitrates are highly soluble and much more easily reduced to ammonia than N2. While this approach may seem promising, it needs to be kept in mind that the industrial process for producing nitrates and nitrates are is from ammonia via the Ostwald process, thus their direct use as precursors for ammonia production is highly circuitous and impractical. Additionally, nitrates / nitrites have limited stability in water hence direct production and on-spot utilisation is desirable. Consequently, the production of NOX via a plasma-driven process for the direct consumption to produce ammonia would be a desirable industrial process, if practicable. The first step in the process of the present invention is the plasma-activation of air, at the water / electrolyte interface, to produce NOx (i.e. a mixture of NO2' and NOs' species). Plasma is essentially an ionized gas composed of a range of species (including electrons, ions, radicals, molecular fragments) at various energy levels. Plasma can be categorized into thermal and non-thermal plasmas (NTP). Thermal plasmas exhibit equilibrium between electrons and bulk gas temperatures (typically higher than 5 x 103 K). Meanwhile, in NTP such equilibrium is not established thus the temperature of the electrons can be several orders of magnitude higher than ambient. NTP is less energy intensive than thermal plasmas, and still possess electrons with high translational energies required to overcome the stability of the N2 molecule via electronic structure transitions, which makes NTP a suitable choice for aforementioned process. Nitrogen activation, and oxidation, is difficult due to the thermodynamic and kinetic stability of nitrogen in the energy required to break the N2 triple bond. Plasma is able to provide sufficient energy to activate N2. This reaction occurs commonly in nature as a consequence of lightning to produce NO. Three key approaches have been studied in orderto drive the plasma-driven generation of NOX species. Figure 1 depicts various configurations of plasma discharge (a) pin to liquid discharge, (b) pin-in-nozzle discharge and (c) bubble discharge. The purpose of these systems is to generate plasma at the liquid / gas interface, producing NOX species which can then be dissolved into the water / electrolyte. There are a range of variables which in can be used to control the (i) amount of species, (ii) the overall energy efficiencies of the system (NOX produced / power input) and (iii) ratio of nitrate to nitrite. These variables include plasma input voltage (amplitude, pulse width and repetition frequency), time, gas flow rate, and liquid flow rate. The impact of these parameters of the performance of the different plasma systems are interrelated. For example, the impact of changing voltage and pulse / discharge frequency on the pin-in-nozzle design on the total quantity of NOX produced is relatively minor, as shown in Figure 2. This is attributed to the mass-transfer of the activated species in the solution being the limiting factor in NOX production, as opposed to the plasma itself. On the other hand, when those mass transfer impacts are overcome, by implementing a bubbler-system of the present invention the impacts of varying parameters become much more significant. Table 1 demonstrates a sample results comparison between the differing designs for plasma NOX generation, specifically comparing the pin-in-nozzle and column bubbler. It is clear that the production rate is significantly higher in the case of the column bubbler, however, in this case the ratio of nitrates / nitrates is notably different. Table 1: NOX generation results for the pin-to-liquid in nozzle enclosure and pin-to-liquid in column bubbler (Refer to Figure 1, b and c, respectively) Pin-to-liquid in nozzle enclosure (b) Pin-to-liquid in column bubbler (c) Power (W) 10 33 Time of operation (min) 15 5 Volume of electrolyte (L) 0.1 0.25 Type of electrolyte Water + 0.1 MHCL Water Air flow rate (L / min) 0.03 1 NO2' concentration (mM) 1.2 0.34 NO3' concentration (mM) 0.5 1.61 NOs" / NO2- ratio 0.41 5.3 Total NOX (mM) 1.7 1.91 Production rate 0.068 0.174 (moles / kWh) Ultimately, the design of the plasma-system, along with the input voltage, frequency, time, gas type and flow rate, humidity and temperature liquid type (i.e. electrolyte / water) and flow rate all have a significant impact on the quantity of NOX, the energy efficiencies of the species produced (NOX produced / power input) as well as the ratio of nitrate to nitrite. Given the teachings in the present specification, it would be expected that variations in design to optimise NOx production would be within the capacity of a person of ordinary skill in the art. Attention was then focussed enhancing energy efficiency with respect to NOX formation. An AC sinusoidal waveform with periodic gaps between discharges was employed as compared to DC plasmas, AC waveform is considered more efficient, inexpensive, and reliable for longer operation. This is because of higher excited state active species at similar powers (in some cases 5 times higher) due to less energy dissipation into heat at the electrodes in aqueous environments. Compared to thermal plasmas, where gas is heated to temperatures typically in order of 20,000 K, the present invention utilized non-thermal (cold) plasma which is generated at ambient temperatures and pressures but still exhibit elevated electron temperatures. The use of underwater plasma bubbles intensifies gas-to-liquid mass transfer, which is assisted by interfacial areas, residence time and internal pressures. Thus, the present inventors developed a nonthermal AC plasma, exploiting a bubble column with varying discharge regimes (including spark and glow discharges). Five different design configurations (Fig. 3A) were tested, with underwater plasma bubbles as the dominating aspect of the design. It is clearly shown in Figure 3A, that the combination of two reactors, exploiting both spark and glow discharges, coupled with Raschig rings resulted in a significant increase in NOX energy efficiency, attaining a NOX generation energy efficiency of 263 mmol kWh’1 which is three times better than the state of the art. The key features of the reactor design (Figure 3B-D), leading to high energy efficiencies are characterised by the combination of (a) multiple discharge schemes (glow and spark discharges) (b) dual reactor configuration within one AC circuit; and (c) bubble dynamics control (Raschig rings). As shown in Figure 3E&F, the OES data indicates that the excited species generated in the glow discharge differ drastically from those in the spark discharge. Within a glow discharge system, NOy is the dominant species (SRGD) produced, whilst with the spark discharge, NO2 is favoured (SRSD). Combining the two forms of discharges within a single unit made efficient utilization of the applied power minimizing energy losses. Further, the implementation of dual reactors (one being the high voltage electrode, the other being the ground), leads to a reduction in energy losses resulting from having the ground reactor within the solution. The incorporation of Raschig rings further increased the energy efficiency. This enhancement can be attributed changes in mass transfer and residence times, allowing for an intensification of mass transfer from the gas phase NOX species into solution. Ultimately, these key design approaches resulted in an energy efficient, scalable approach to aqueous NOX production. Once the NOX (nitrate / nitrite mixture) is produced from the plasma, it needs to be reduced and the method chosen in the present case is electrocatalytic reduction. In order to better understand the system, and, the ability of the NOX intermediaries to be electrocatalytically reduced to ammonia, the present inventors initially focused on H-cell experiments. In these experiments, the electrocatalytic conversion of NOxto ammonia was performed using an integrated system that incorporates a customdesign plasma-bubbler to the electrochemical H-cell, as well as with NOX salts, to understand the electrocatalytic conversion pathways. The conversion of NOxspecies can produce ammonia at higher rates and faradaic efficiencies than N2 directly. In acidic media, the reaction proceeds as shown in Equations 1-3 below. The reaction competes with the hydrogen evolution reaction (HER), Equation 4. Whilst HER occurs at more negative potenital than the nitrate / nitrite reduction, slow kinetics for nitrate / nitrite reduction may lead to HER occurrence and it has been found that unwanted HER may be addressed by electocatalytic optimization. NOj + 2H+ + 2e“ -> NO2 +H2O NO3 + 10H+ + 8e" NHZ + 3H2O NO2 + 8H+ + 6e“ -> NHZ + ?H20 2H+ + 2e~ -> H2 E° = 0.83 V vs NHE E° = 1.02 V vs RHE (1) E° = 0.87 V vs NHE E° = 0.93 V vs RHE (2) E° = 0.86 V vs RHE (3) E° = 0 7vsNHE E° = 0 V vs RHE (4) Thus, the different pathways for the conversion of NOX, the competing HER as well as different reactants (NO3 and NO2) mean that catalyst design for ammonia synthesis requires careful consideration. The present invention has established that a range of transtion metals can be used to facilitate the electrocatalytic conversion of ntrogen to ammonia. Of these copper and nickel were the most preferred. The description of the electrocatalyst will be provided with reference to copper but it will be appreciated that it can apply to other transition metals. In the present invention, astound in Figure 4, Cu foil is capable of effectively converting NOxto ammonia at high Faradaic efficiencies with high production rates. By studying a number of forms of copper, such as Cu foam, Cu nanostructures and single atom Cu catalysts, a clear correlation between Cu surface chemistry and surface area can be established. A range of Cu-based catalysts was prepared and evaluated fortheir performance forthe electrocatalytic conversion of NOxto ammonia (Cu foil, foam and nanowires (NWs) grown on foam). Representative scanning electron microscopy (SEM) images of the Cu NWs (Fig. 5 C&D) supports the existence of a nanoporous morphology of uniformly dispersed thin nanowires on the copper foam. It is clear from these images that the Cu NWs seed out from the metallic Cu skeleton of the porous background foam during electrode preparation. It was found that the Cu NWs sample was able to attain the highest current density ( / ) for the reduction of plasma-activated electrolyte whilst achieving an ammonia production rate of 45 nmol.S’1.cm’2 and Faradaic efficiency (FE) of ~100%. Comparatively, the Cu foil and foam facilitated somewhat lower FEs of ~80 and 71%, respectively, with ammonia yields of 6.0 nmoLsTcm-2 and 8.9 nmol.sTcm-2 (at -0.5 V). This variation in catalytic activity can be ascribed to the variation in electrochemical active surface area (ECSA) between the electrodes. The ECSA for the Cu NWs catalyst was significantly larger for the foil and foam samples, indicating an increase in active sites for the NWs sample, ultimately improving the overall yield of ammonia. The high FE is due to the presence of Cu1+ / Cu° is well-known for the suppression of the competing hydrogen evolution reaction HER, which is the breakdown of water into oxygen and hydrogen. To understand the origin of the NH3, in particular whether it arises from NOx or dissolved N2 reduction, control experiments were performed showing that the electrolyte alone (with no plasma activation) resulted in no NH3 production. Furthermore, the polarisation curves (Fig. 5E) revealed that the Cu NWs electrode facilitated a very high current density ( / ), attaining a j of-45 mA cm 2at-1 V (compared to 28 mA cm 2 for the blank electrolyte). This indicates that the current obtained arises from eNRR and not from competing HER. Fig. 5F displays the dependence of ammonia production rate and FE for NOx reduction on applied potential (each electrolysis duration was 0.25 h). As the potential was changed from 0.2 V to -0.6 V, the ammonia production rate increased along with the FE (from 5% at 0.2 V to ~100%). The lower FE (<100%) between 0.2 V to -0.2 V can be ascribed to some charge loss arising from the conversion to NO3 to NO2 species. During NO3 reduction, adsorbed *NO2 was identified as a key intermediary. It was observed a portion of the *NO2 desorbed into the solution as NO2' at lower potentials, hence the observed lower FE at lower potentials (between 0.2 to -0.2 V). At higher potentials, however, the conversion rate of both nitrate and nitrite to ammonia is very high, which compensates for this side reaction. To further understand the reaction pathway, and the consumption of both nitrate and nitrite as a function of electrolysis duration, a batch experiment was undertaken with a successive sampling of nitrite, nitrate and ammonia (Fig. 5G). With an extended reaction time of 2.5h, both NOs-and NO2 species were exhausted entirely (from 2.7 mM and 1 mM, respectively). On the other hand, ammonia concentration increases from 0 mM to 3.5 mM over the same period. The total concentration of N-species remained constant during electrolysis. Moreover, the chronoamperometric / 4 curve displays a consistently declining j which indicates the consumption of reactants during eNRR. Throughout the prolong experiment the FE remained at ~100% for the first 1 h then slowly declined as the reactive NOx are consumed and converted completely into ammonia. Importantly, post-reaction assessment of the Cu NWs cathode through X-ray photoelectron spectroscopy (XPS) revealed no noticeable chemical changes of the electrode. Moreover, the N1s spectrum did not indicate any nitrogen bonded to the surface of the cathode, indicating the non-poisoning interaction of the NOx reactive species with the catalyst. It is highly desirable to integrate the plasma-driven production of NOxwith the electrocatalytic system for the production of ammonia. The stability of the produced nitrate / nitrites is low and thus the direct conversion of the activated species to ammonia is highly desirable. Two possible approaches to integrating the plasma / electrocatalytic systems as shown in Figure 6. Figure 6a displays the incorporation of the plasma-bubbler to a batch-type H-cell system, used for lab scale validation. Figure 6b shows flow through system with the plasma-bubbler having a liquid outlet leading to a flow through electrolyser to convert the NOxto ammonia. It should be noted that the optimization of the NOX production, relative to the NOx consumption in the electrolyser is required to maximize production and overall energy efficiency. A further benefit to note is the direct production of fertilizer (i.e. ammonium nitrate) from the system. The integration is rather intricate because of simultaneous electrodynamic of both AC-driven plasma source and DC-driven electrocatalysis source. This requires appropriately balancing the current flow within the two aforementioned electric circuits as well as mass and energy balances for achieving optimal throughputs. When the appropriate production / consumption balances are put in place, it is possible to directly produce ammonium nitrate from the conversion. Alternative embodiments are envisaged in which a reservoir is provided intermediate the NOx generation vessel and the NOx reduction vessel. A reservoir can provide benefits in terms of feeding the NOx for reduction at a predetermined rate, which can avoid build-up of NOx or NOx starvation at the site of electrocatalytic reduction. The present system was tested and it was established that an increase in cell voltage from 1 V to 1.4 V resulted in an increase in j from 27 mA cm 2 to 52 mA cm 2 and ammonia rate from 15 mg h1 to up to 24 mg h1. Furthermore, the stability of the flow system at a current density of 30 mA cm 2 was investigated, where plasma-activated electrolyte was fed continuously while ammonia was collected from the outlet. The hybrid system maintained a stable applied cell voltage of 1.5±0.04 V and an average Faradaic efficiency of ~58% for 8 h continuously (Fig. 7C). The electrochemical conversion of the resultant NOx intermediaries, using a scalable electrolyser, resulted in current densities of over 50 mA / cm2, Faradaic efficiencies of ~60%, an ammonia production rate of 23.2 mg / h (42.1 nmol / scm2) at a very low cell voltage of 1.4 V. Figure 7B compares the overall production rate of ammonia with recently reported state-of-art results for eNRR, Li-intermediary NRR, and plasma-assisted NRR demonstrated at ambient conditions. The NOx intermediary approach developed in this study is shown to facilitate the highest potential to yield high rates of ammonia while maintaining high energy efficiency. The ammonia yield rate is between one to three orders of magnitude higher than every other electrochemical method (at similar reaction geometric areas). When scaled up using an electrolyser, the rate increased by another order of magnitude. At the same time this hybrid system is characterized by much reduced power consumption (total of 253 kWh / kg NH3) compared to plasma-assisted ammonia production technologies. This is between one to three orders of magnitude less energy-intensive than plasma assisted electrochemical conversion of nitrogen to ammonia and gas-phase Dielectric Barrier Discharge (DBD) synthesis method. The energy consumption is also better than the studies that showed relatively high yield ammonia production via Li-intermediary approaches. In the case of eNRR, no practical method has been demonstrated until now to show a considerable production rate and FE, making those systems unfavourable for scaling. EXAMPLES GENERAL EXPERIMENTAL Materials All reagents and solvents were purchased from Sigma-Aldrich or from Chem-Supply Pty Ltd. Cu foam was purchased from Xiamen TMAX Machine Limited. Oakton pH / lon 700 Ion 700 Benchtop Meter and Cole-Parmer Combination Ion Selective Electrodes (nitrate) were purchased from John Morris Group. Milli-Q water with a resistivity of 18.2 MQ.cm was obtained from an inline Millipore RiOs / Origin H2O purification system, was used throughout the experiments for sample preparation and reaction. Copper nanowires (Cu NWs) fabrication. The commercial Cu foam and foil was cut into desired sizes and ultrasonically cleaned with acetone, ethanol, and finally Milli-Q water for 15 min intervals, and then washed with dilute H2SO4 solution to remove any surface impurities and oxide layers. Cu(OH)2 nanowires were first synthesized on Cu foam by immersion into a solution containing 0.133M (NH4)2S2Ob (ammonium persulfate) and 2.667m NaOH for 0.5 h at room temperature. Subsequently, the Cu foam was removed out from solution, rinsed with Milli-Q water and absolute ethanol, and air-dried. CuO NWs were then fabricated by annealing the prepared Cu(OH)2 NW arrays at 180°C for 1 h in air. The resulting CuO NW sample was electrochemically reduced to CU / CU2O NW arrays in 0.5M Na2SO4 under-1V vs RHE. Electrochemical evaluation. All electrochemical evaluations were conducted using Autolab Potentiostat (Autolab M204) in a custom-designed H-type electrochemical cell and electrolyser. The cathodic chamber was separated from the anodic chamber by Nafion@117 membrane. For the H-type cell, a three-electrode set-up using the Cu catalyst (foil, foam and Cu NWs) as the working electrode (WE), platinum wire as the counter electrode (CE) and Ag / AgCI (sat. KCI) reference electrode (RE) was used. 10 mM H2SO4 was used as the background electrolyte in this study, and the optimization of acid concentration was performed. Typically, for the H-type cell studies, 50 mL of electrolyte was used in the cathodic chamber to allow for electrolyte sampling. The electrode size for the H-cell was 1cm 2 and Cu foil was used for optimization studies. The reaction was facilitated with magnetic stirrer at the speed of 650 rpm. All potentials for H-type cell were described versus the reversible hydrogen electrode (RHE) via the following equation: Erhe = E^g^gci) + 0.197 + 0.059 x pH (pH = 1.68 in this study) To further translate this concept for large scale application, the plasma-activated water (PAW) from the scaled-up reactor (vide infra) was fed into a high throughput electrolyser to understand the potential for ammonia production rate and yield. A membrane electrode assembly (MEA) was prepared by sandwiching the Cu NWs cathode (electrode size 9 cm2) and Ru / TiO2 anode between a commercial Nation membrane. The MEA was loaded within the electrolyser with PAW being used as the catholyte and 0.1 M H2SO4 as the anolyte (using a peristaltic pump with a flow rate of 1.5 mL / min). For the electrolyser optimization, 250mL of the PAW was circulated in the cathodic chamber. For the stability test, a continuous flow was used for 8 h with 30 mA.cnrr2 being applied. Ammonia (NH3) detection by the indophenol blue method. From the cathodic chamber electrolyte solution, 0.5 mL of electrolyte was taken and transferred into a 2 mL sample tube. Into the tube, 0.4 mL of 1 M NaOH solution (with 5 wt.% salicylic acid and 5 wt.% sodium citrate), 0.1 mL of 0.05 M NaCIO and 30 pL of 1 wt.% C5FeNeNa2O (sodium nitroferricyanide) in water was added. The mixture was then incubated in the dark at room temperature for 2 h prior to UV-Vis testing. The concentration of ammonia was determined via a calibration curve. The calibration curve was prepared using a set of standard solutions with a known amount of (NH4)2SO4 (concentrations were based on NH4+) in 10 mM H2SO4. Into these solutions, the above-mentioned indophenol blue reagents were added, and the indophenol blue absorbance at 655 nm was determined after 2 h. The limit of detection (LOD) of UV-Vis used in this study refers to the absorbance at 655nm obtained from blank 10 mM H2S04forthe lower limit and from 200 pM NH4+ for the upper limit. Nitrite (NO2') detection by Griess Reagent. 50 pL of the sample was taken and transferred into a cuvette and combined with 50 pL of Griess Reagent and 0.9 mL of Milli-Q water. The resulting sample was mixed thoroughly. The mixture was incubated at room temperature in the dark for 0.5 h prior to UV-Vis testing. Solutions of NaNO2 with known concentrations (in 10 mM H2SO4) were used as calibration standards, with the absorbance at 525 nm used to plot the calibration curves. Upper LOD of UV-Vis used in this study refers to the absorbance at 525 nm obtained from 200 pM NaNO2. A dilution factor was applied to measure nitrite concentration in plasma-activated water (PAW). Nitrate (NO3) detection by ion-selective electrode. An ion-selective electrode (ISE), also known as a specific ion electrode (SIE), is a transducer (or sensor) that converts the activity of a specific ion dissolved in a solution into an electrical potential. The voltage is theoretically dependent on the logarithm of the ionic activity, according to the Nernst equation. Cole Palmer Nitrate selective probe has a concentration range of 7pM to 1M (0.5 to 62,000ppm). The ionic strength of ion solutions varies with the concentration of the ion to be measured. To maintain a constant ionic strength, an Ionic Strength Adjuster (ISA) is added. This ensures the total ionic strength is independent of the analyte concentration. In this study, 2M ammonium sulfate (NH4)2SO4 was added, as the ISA, at 400 pL to each 20 mL of standard or sample to adjust the ionic strength to about 0.12 M. H2 detection by gas chromatograph (GC). H2 detection was tested by GC (Shimidzu, Model 2010 Plus) equipped with both thermal conductivity detector (TCD) and flame ionization detector (FID) detectors. Physical characterization X-ray photoelectron spectroscopy (XPS) was performed on a Thermo Scientific K-Alpha X-ray spectrometer. The morphology and structure of Cu NWs were imaged by scanning electron microscopy (SEM) using a JEOL JSM-IT-500 HR. UV-Vis absorption spectra were recorded on a Shimadzu UV-3600 UV-VIS-NIR spectrophotometer. Faradaic efficiency and production rate calculations The two crucial descriptors, revealing ammonia synthesis performance, are the Faradaic efficiency and the ammonia production rate. The Faradaic efficiency indicates the selectivity of the electrocatalysis for ammonia synthesis, which refers to the ratio of the electrical energy consumed for the synthesis of ammonia to the overall energy through the electrochemical system. The Faradaic efficiency ( / 7) of ammonia synthesis was determined by Eq. (S1), where n is the figure of the desired electrons for synthesizing one ammonia molecule (n = 6 when ammonia is from nitrite and n = 8 when ammonia is from nitrate), F is the Faraday constant (F = 96485.33), C is the detected ammonia molar concentration, V is the electrolyte volume, and Q is the overall electrical energy travelled over the electrodes. To calculate the number of the exchanged electron, both nitrite and nitrate concentrations were measured before and after each reaction; the average found to be 7.6. For the reactions that both nitrite and nitrate are fully exhausted, n was calculated based on their initial ratio. Ammonia production rate (R) is the ammonia production over unit time and over unit electrode surface area. It can be determined by Eq. (S2), where C is the detected ammonia molar concentration, V is the electrolyte volume, t is the reaction time, and S is the catalytically active surface area of the electrode. c-v Plasma activation of water in the H-cell. Ground-state nitrogen molecules exhibit high ionization potential making it intrinsically unreactive from a thermodynamic standpoint. Still, plasma activation provides avenues for the conversion of highly stable nitrogen molecules into easier to breakdown intermediaries (NOX). Plasma can be categorized into thermal and non-thermal plasmas (NTP). Thermal plasmas exhibit equilibrium between electrons and bulk gas temperatures (typically higher than 5 x 103 K). Meanwhile, in NTP such equilibrium is not established; thus the temperature of the electrons can be several orders of magnitude higher than ambient. NTP is less energy-intensive than thermal plasmas, and still possess electrons with high translational energies required to overcome the stability of the N2 molecule via electronic structure transitions, which makes NTP a suitable choice for the aforementioned process. The design of the plasma-system, along with the input voltage, frequency, time, gas type and flow rate, liquid type (i.e. electrolyte / water) and flow rate all have a significant impact on the quantity of NOX, the energy efficiencies of the species produced (NOX produced / power input) as well as the ratio of nitrate to nitrite. For the batch electrochemical tests, custom plasma bubbler was used in an H-cell and connected to the plasma generator (‘Leap 100’ from PlasmaLeap Technologies). The optimized plasma generator parameters were using a voltage of 100V, duty of 83ps, discharge frequency of 600Hz and resonance frequency of 60kHz. Dry air (Coregas, dry air) was introduced from the top of the custom plasma bubbler at 20 mL / min to generate PAW. The plasma activation was performed for 0.5 h to achieve NOX concentration of~4mM in 100 mL water. PLASMA DISCHARGE DESIGN Plasma reactors, discharge schemes and configurations. Five reactor design configurations using underwater plasma bubbles were tested. Photographs of plasma bubble column reactors design configurations are shown in Fig 8, were: (a) single reactor glow discharge (SRGD); (b) single reactor spark discharge (SRSD); (c) single reactor glow and spark discharge (SRGSD); (d) double reactor glow and spark discharge (DRGSD); and (e) DRGSD with Raschig rings. Plasma bubble column reactors were capable of dual-discharge mode operation, i.e. glow and spark discharge. To achieve the former, the high voltage electrode was sheathed with borosilicate. The latter incorporated a sharpened high voltage electrode with a 1 cm protrusion which induced a spark extending longitudinally towards the bubbles. Meanwhile, combinative discharge reactors coupled both these concepts in a single unit. In configurations involving single reactor, water was used as ground, meanwhile double-reactor configurations utilized secondary plasma reactor as ground. Plasma reactors were fabricated using a quartz tube with one end sealed and 12 laser-drilled holes with a diameter of 200pm located radially 5 mm above the sealed base. Stainless steel rod was used as high voltage electrode inserted concentrically into the quartz tube. A tee fitting was connected to the quartz tube to position the electrodes. Instrument grade air was injected as the feed gas at a flow rate of 1 L / min in each reactor via a mass flow controller. Reactors were powered by plasma generator (‘Leap100’, PlasmaLeap Technologies) capable of yielding voltage output of 0-80 kV (peak-to-peak), discharge power of up to 700 W, and a discharge frequency range of 100 Hz-3000 Hz. For all experiments, power was provided in form of batches of sinusoidal pulses with a lag time between each batch. Resonance frequency of pulse was set at 60 kHz while discharge frequency of each batch of pulses was 300 Hz (duty cycle of 103 ps). Electrical and optical measurements. A digital oscilloscope (DS6104, Rigol) was employed to record both the sinusoidal voltage and current waveform via a high voltage probe (PVM-6, North Star) and a current probe (4100, Pearson), respectively. The time-averaged discharge power (P) was calculated from the measured discharge voltage and current with the following formula: rt0+T P = f u(t)i(t)dt 'to The electrical parameters across various reactor configurations are presented in Table 2. Optical Emission Spectra (OES) were recorded using a spectrometer (SR-500i-A-R, Andor Shamrock), with a grating groove of 300 lines mm 1 and exposure time of 20 ms. Table 2: Operational conditions of plasma reactors and production rates of species Voltage amplitude (kV) Current amplitude (A) Power (W) Operation time (min) Mean NO3 (PPm) Mean NO2 (PPm) Conductivity (pS / cm) PH SRGD 12.5 0.38 7.38 10 4.6 0 37.70 4.02 SRSD 9.8 0.5 9.22 10 1.8 4.8 38.37 4.00 SRGSD 8.7 1.56 10.67 10 9.9 7 107.47 3.54 DRGSD 8.5 1.68 11.27 10 20.2 4.5 170.20 3.37 DRGSD + Raschig rings 8.4 1.68 11.27 ★ 10 24.9 4.3 209.90 3.29 Using an AC system was desirable as polarity inversion in AC systems prompts current passing through zero at half cycle which enhances the lifetime of electrodes. Cold plasma is particularly useful to selectively transfer incident electric power to the electrons rather than volumetric heating of the entire gas as it is an energy-efficient route to formation of active species via collisions. Without wishing to be bound by theory, it is believed that higher production of reactive radicals in the aqueous phase takes place because of mechanical agitation and local heating caused by bursting of bubbles. Figure 9 shows the plasma processes arising from Spark and Glow plasma ionization of N2, and the species generated at the interface. Single reactor glow discharge (SRGD) was operated at glow-only discharge scheme by applying 7.38 W power and using a dielectric barrier around the high voltage electrode. In principle, the use of dielectric barrier limits the flow of charge enabling higher voltages at the same power. In such discharge scheme, production of NO3 predominated over NO2, which corroborates with literature. Meanwhile, spark-only discharge scheme was dominated by NO2 over NO3, and higher current to voltage ratios than the glow-only scheme and comparatively higher power (9.22 W). High intensity electric fields in glow discharge scheme favour ozone production, which maintain oxidation environment the entire volume in the tube facilitating conversion of NO2 to NO3. However, spark streamers are confined in the concentrated volume prompting formation of high energy species and back-reactions of NO3 to NO2. Thus, the underwater plasma bubbler reactors of the present invention , combine both glow and spark discharges to generate the NOX intermediaries at the unprecedented energy efficiency of 263 mmol / kWh. It should be noted that the above sections outline the use of air as the inlet gas, however, to date a range of different gases have been examined. It is possible to use any gas and tune the plasma / inlet parameters to obtain the desired product. In the present specification, the results presented are predominantly for the use of air, however mixtures of N2 / O2, along with H2O also show promise. It should be further noted that the system has also been adapted for use for CO2 conversion showing favourable results. CATALYST Incorporation of catalyst into the plasma system The incorporation of a catalyst into the glow and / or spark discharge region for the plasma-driven NOx generation. Figure 10 below displays the impact of incorporating a metal oxide (TiO2) with an appropriate binder (Graphene Oxide, GO) for the plasma-driven NOx synthesis. It can be seen that total NOx production rate was increased by ~50% and the concentration of GO has negligible effect on the performance. GO works as the binder for shaping the metal oxide catalyst as the packing for plasma reactor system. As mentioned above, transition metal catalysts, an specifically copper, nickel, tin, iron, bismuth, cobalt, titanium and oxides thereof are particularly useful in the present invention. Any suitable catalyst binder, such as silica, alumina, clays, polymers or carbon based supports can be used. Physical characterization of catalytic sites To probe the active sites responsible for eNRR, XPS analysis was carried out on the post-reaction Cu NW electrode to investigate any variation in the surface chemical state of the electrode owing from the negative bias applied herein. From Figure 11 it can be seen that the Cu2+ species are reduced to Cu1+ / Cu° (indicated by the peak shift to 932.6 eV). On the basis of these results and eNRR data, and without wishing to be bound by theory, it is believed that these interfaces are playing the role of active sites for eNRR reaction. It is understood that the formation of Cu1+ / Cu° interfaces in Cu-based catalysts leads to a suppression of the competing hydrogen evolution reaction (HER) during eNRR. Further, these interfaces promote eNRR by reducing the free energy barrier for ammonia formation through nitrate and nitrite ions. The XPS results reveal that the surface of the nanowires comprises of mostly of CuO species, evident from the high-resolution Cu 2ps / 2 spectra which show a large peak at binding energy 933.7 eV which is ascribed to Cu2+. Figure 12, showing the N1s spectra, clearly indicates that there was no nitrogen attachment to the surface of post-reaction Cu NW electrode. This indicates that the Cu NWs catalyst did not suffer from poisoning by the reactant NOX species and supports the stability of the catalyst. NOX ANALYSIS Calibration plot and background determination A number of calibration and control experiments were conducted using UV-visible spectroscopy to investigate the background of NH3 and NOx in the used electrolytes, PAW, solutions and electrodes, It was observed that a in some bubbler configurations a barely detectable amount of ammonia is generated at the rate of 0.21 nmol s-1 during the plasma activation, however, with the plasma column bubbler, no ammonia could be detected in the electrolyte, showing the specificity of the preferred embodiments of the invention to be specific toward the production of NOX. In the case of the electrolysis of PAW, the significant production rate of 45nmol cm~2S“1 was obtained. Moreover, the measured concentration of ammonia in the background electrolyte, as well as all of the other controls, was more than four orders of magnitudes lower than the measured ammonia in the electrolysis tests. This result indicates that the environmental contaminations are not contributing to the ammonia production rate reported in this work. BUILD UP OF NOX SPECIES OVER TIME The concentration of NOX was controlled by the plasma activation time under the optimized parameters (voltage of 100V, duty of 83ps, discharge frequency of 600Hz and resonance frequency of 60Hz). It is shown from Figure 13, the total amount of NOX increases linearly as a function of plasma activation time. In this study, 0.5 h of plasma activation (produces ~ 4mM NOX in 100 mL of water) was selected for the electrolysis tests. This plasma activation time was selected based on the systematic study on the effect of NOX concentration (using nitrate and nitrite salts) on the FE and production rate of ammonia (Figure 15). Electrochemical optimization The first step toward the optimization of the electrocatalytic conversion of NOX to ammonia was performed using nitrate (KNO3) and nitrite (NaNCh) salts as the NOX source, and Cu foil (1cm x 1cm) as the cathode, Pt wire as the anode and Ag / AgCI (sat. KCI) as the reference electrode in a custom-designed H-cell (Figure 5B). In acidic media, the reaction proceeds, as shown in Equations S1-S2 below. The reaction competes with the hydrogen evolution reaction (HER), Equation S3[1], NO3 +10H++ 8e~  NH£+ 3H20                 E° = 0.93 V vs RHE        (Eq. S1) NO2 + 8H++ 6e~  NH / + 2H2O                 E° = 0.86 V vs RHE        (Eq. S2) 2H+ + 2e~^H2                        £^ = 07 vs RHE         (Eq. S3) Whilst H+ is required to facilitate the reaction, a high concentration of H+ may result in occurrence of HER. In the present experiment, when H+ was not available in the electrolyte, both FE and ammonia yield rate was very low (> 30% and 1 nm cm 2s’1, respectively). The addition of acid (10mM H2SO4) in the electrolyte resulted in a significant increase in the ammonia production rate and FE, from 0.81 to 8.94 nmolcm'2S'1 and from 31% to 73%, respectively. However, a further increase in the acid concentration did not positively impact the ammonia production while the FE dropped significantly as HER became more competitive. See figure 14. Therefore, in this study, 10mM H2SO4 was used as the background electrolyte which (a) increases the conductivity of the electrochemical system to minimize energy losses caused by the resistance; (b) provides proton for ammonia synthesis; (c) supports synthesis of ammonium sulphate (NH4)2SO4 which is soluble in water and can be used directly as a fertilizer. See figure 15 When nitrite was used as the reactant, ammonia production rate increased with more negative potentials, and the rate reaches its maximum at -0.5V with FE of about 73%. While for nitrate, its maximum production rate (~3.8 nmol cm 2s-1) and FE (~60%) occurred at -0.4V. Beyond the optimal potential, both rate and FE start to decrease due to a possible occurrence of HER. Figure 16 compares the LSV curves of nitrate and nitrite salts in 10 mM H2SO4. The reduction of nitrate to nitrite (Eq. S4) is evidenced by a peak occurred at around -0.25V on the LSV curve of the nitrate solution (1 mM KNO3). NO3 + 2H++ 2e~NO2 + H2O                       (Eq. S4) This result indicates that at lower potentials, nitrate is more favourable to be converted to nitrite rather than ammonia (which is in agreement with the literature [2]). To investigate, a 15min electrolysis experiment was conducted in 25 mL of 1 mM KNO3 solution at -0.3V. It was found that 0.7 pmol of ammonia was produced, while 1.17 pmol of nitrite was produced in this potential. On the other hand, when the experiment was performed at -0.5V, 1.64 pmol ammonia and 0.66 pmol nitrite were produced. During NOX reduction, it established that NOs" is first adsorbed to the surface of the electrode to form *NOsand the N-O bond is then spontaneously cleaved stepwise producing *NO2 and *NO. Next, the hydrogenation of *NO to form *NOH occurs. Successively, the *NOH hydrogenated to form *NH2OH and then transformed into *NHs. Finally, *NHs desorbed from the catalyst. In this process it was observed that a portion of the *NO2 desorbed into the solution as NO2' at lower potentials. This clarifies the reason behind the observed lower FE of ammonia conversion at the lower potentials. At higher potentials, however, the conversion rate of both nitrate and nitrite to ammonia is very high, which compensates for this side reaction. To investigate the effect of NOX concentration on the ammonia production rate and FE, a range of concentrations of nitrite and nitrate salts was tested (Figure 17). In the case of NO2- salt, much higher production rate and FE were observed compared to NOs- salt. Please note, the FE of the conversion of NCh to ammonia can reach 100% while the FE of NOs- stays at around 60%. The lower FE when NO3 was used can be ascribed to some charge lose arising from the conversion to NO3 to NO2 species instead of ammonia. However, both NOs' and NO2' are converted to ammonia in the end. For both nitrite and nitrate, ammonia production rates and FE increased significantly when the concentration reached at ~1 mM. This graph was a guide to set the duration of the plasma activation (achieving NOX concentration of >1 mM) to maximize the ammonia production rate and FE. Effect of pH upon electrolysis A comparative study was carried out in which a series of electrocatalytic reduction reactions were carried out under identical conditions, save for varying the starting pH. Table 3 displays the corresponding experimental conditions. Table 3: Conditions of ammonia production rate data results Experiment Condition Electrode Working CU / CU2O NWs on Cu Foam, 1cm2 (electro-reduced from CuO NWs) Counter Pt Reference Ag / AgCI Electrolyte PH 1.68 (no acid added, low pH was caused by plasma) KCI concentration 50mM Electrolysis Electrolyte Volume 25mL Time 15min Applied Potentials from -0.3V to -0.7V vs RHE Stirring Speed 650 rpm Analysis was undertaken with a range of pH conditions. For example, plasma activated water (PAW), salt (KCI) with a concentration of 50mM was added to PAW, allowing the electrolysis to occur in a neutral media. From this and other experiments, the present inventors have concluded that the reduction method of the present invention may be carried out at any pH. Figure 18 displays the ammonia production rate of the system. Catalyst surface area effect To compare copper-based catalyst performance as a function of available surface area, control experiments were performed with Cu foil and Cu foam. Cu NWs electrode facilitated a very high current density (j), -45 mA cm 2 at -1V, compared to -22 mA cm 2 for Cu foil and -26 mA cm 2 for Cu foam. Cu NWs also facilitated a much higher catalytic activity for ammonia synthesis with a production rate of 40±3.3 nmol cm 2 S'1 and FE of 100±7%. At the same time, Cu foil only provided ammonia production rate of 6.1 ±0.6 nmol cm2 s 1 with FE of 80.6±0.3% and Cu foam had a rate of 8.8±1.3 nmol cm-2 S’1 with FE of 71.1±1.7%. See Figure 19 In the case of Cu foil and Cu foam, non-Faradaic charging currents are measured in the potential range of 0.5V and 0.55V vs RHE and for Cu NWs, the potential range is 0.25V to 0.30V vs RHE. The scan rate is varied between 5,10,15, 20 and 25 mV / s and the anodic (positive) and cathodic (negative) current densities are obtained from the double layer charge / discharge curves at 0.525V vs RHE for Cu foil and Cu foam and 0.275V vs RHE for Cu NWs. See Figure 20. The double-layer capacitance was then calculated by averaging the absolute values of cathodic and anodic current densities and take the slopes of the linear fits. The slopes obtained with Cu foil, Cu foam and Cu NWs are 0.13mF / cm2, 3.03mF / cm2 and 15.24mF / cm2 respectively, indicating that the fabricated catalyst Cu NWs has much larger electrochemical active surface area compared to the commercial Cu foil and Cu foam. Catalyst species The performance of a nickel based and single-atom copper catalysts in the electrocatalytic reduction of nitrate to ammonia were investigated and the results are shown in Figures 21 and 22. These results confirmed the efficacy of different transition metals, and catalyst types in the electrocatalytic reduction of the present invention REDUCTION OF NOX SPECIES OVER TIME With an extended reaction time of 2.5h (See figure 23), both NOs and NO2'species were completely exhausted (from 2.7 mM and 1 mM, respectively). On the other hand, ammonia concentration increases from 0 mM to 3.5 mM over the same period. A slightly lower final concentration of ammonia compared to initial concentration of NOxwas obtained (3.5 vs 3.7 mM). This reduction can be attributed to the loss of a small amount of NOx and ammonia due to sampling. The chronoamperometric i-t curve displays a consistently declining j which indicates the consumption of the reactants during this 2.5h. NMR analysis (see Figure 24) also supports the formation of ammonia with non-detection amount in the PAW solution before electrocatalysis. In general, the peak for N2H4 occurs at the chemical shift of 3.2 ppm and the result indicates that there is no N2H4 in the final solution. There are two other small peaks are ascribed to -CH3 and -CH2 respectively, (-OH is the main peak with water as the background solution), which is caused by the impurity of ethanol. CO2 REDUCTION A similar series of experiments was conducted to those described above, with the input gas changed from air to carbon dioxide reduction, in order to investigate carbon dioxide reduction. Plasma runs were conducted for 10 minutes by continuously bubbling CO2 gas through Milli-Q water at 0.1-0.5 L min-1. For these tests, Plasma Leap was operated at voltage of 200 V, duty cycle of 83 ps, discharge frequency of 2 kHz and resonance frequency of 60 kHz. Subsequently, activated species in liquid phase were electrochemically converted to hydrocarbon products. Two different catalysts, i.e. Cu foam and Ni, were selected as cathodes. While CO2 to CO conversion was prevalent, some higher hydrocarbons produced. The tests evidenced that the invention can be successfully utilized for CO2 conversion to high value chemicals. TECHNO-ECONOMIC CALCULATIONS The global $60 billion ammonia fertiliser market is supplied by ammonia generated using the conventional Haber-Bosch process at an average price of $0.23-25 per kg. Locally, the price ranges from $0.2-$0.5 per kg of ammonia. Due to the advantages experienced by large plants due to economies of scale, almost all fertilizer plants are large-scale (~100,000 MT per year), located strategically near ports for water requirement as well as for shipping and as a result, a significant infrastructure is required to transport fertilizer to rural farms and locations. Hence, local farmers are required to pay a significantly higher price, i.e. 5 kg of ammonia fertilizer costs $10.58. (AUD as at September 2020) As such, considerable efforts are in place to generate ammonia in small-scale delocalized units at a competitive cost. While electrochemical nitrogen reduction reactions to ammonia are proposed as a promising technology, the best performing NRR catalyst can generate ammonia with a low yield of merely 0.23 pmol lr1cm-2 at RTP, with a high energy input of 1410 kWh / kgNH3. It must be stated that in addition to the high cost, the overall yield within these electrochemical NRR are very low, making these systems unfavourable for scalability. In contrast, the hybrid NRR system of the present invention is capable of generating ammonia with a yield which is ~3,000 times greater than the NRR counterpart. As indicated in Figure 5, using a pinnozzle plasma design and in a H-cell, the hybrid system of the present invention is capable of generating 5 ammonia with the pin-to-liquid bubbler column plasma system generating NOx at 3.8 kWh / mol, which is at least three times more energy-efficient than state of the art. The flow-through electrolyzer can produce ammonia directly with specific energy consumption as low as 0.19 kWh / mol ammonia. 10

Claims

1. A method of reducing a gaseous compound comprising the steps of: subjecting the gaseous compound to plasma forming conditions to form a plasma; contacting the plasma with water or an electrolyte at a plasma-water or electrolyte-water interface, thereby to provide a dissolved plasma derived species; and electrocatalytically reducing said dissolved plasma derived species to provide a reduced compound.

2. A method according to claim 1 wherein the gaseous compound is an oxygen containing compound or is mixed with oxygen.

3. A method according to claim 1 wherein the gaseous compound is carbon dioxide.

4. A method according to claim 1 wherein the gaseous compound is nitrogen mixed with oxygen.

5. A method according to any one of the preceding claims wherein the plasma is generated by acombination of glow discharge and spark discharge in a configuration of a pin-to-liquid with no enclosure, pin-to-liquid with nozzle enclosure, or a pin-to-liquid with a column bubbler enclosure.

6. A method according to any one of the preceding claims wherein the plasma-water or electrolyte water interface is at the interface of a bubble of gas in the water or electrolyte.

7. A method according to any one of the preceding claims wherein the gaseous compound is provided at controlled humidity.

8. A method according to any one of the preceding claims wherein the water or electrolyte is provided at a controlled temperature.

9. A method according to any one of the preceding claims wherein the water or electrolyte is provided at a controlled pH.

10. A method according to any one of the preceding claims wherein the electrocatalytic reduction is undertaken at either acidic, neutral or alkaline pH.

11. A method according to any one of the preceding claims wherein the electrocatalytic reduction occurs at elevated temperatures (25°C to 90°C).

12. A method according to any one of the preceding claims wherein the dissolved plasma species is stored in a reservoir prior to electrocatalytic reduction.

13. A method according to the above where the solution in the reservoir is dosed to adjusted pH and conductivity prior to electrocatalytic reduction.

14. A method of reducing nitrogen containing gas to produce ammonia, the method comprising the steps of:subjecting the nitrogen containing gas to plasma forming conditions to form a nitrogen containing plasma;contacting the nitrogen containing plasma with water or an electrolyte at a plasma-water or electrolytewater interface, thereby to provide dissolved NOX species; and electrocatalytically reducing said NOxto provide ammonia.

15. A method according to claim 14 wherein the nitrogen containing gas is N2.

16. A method according to claim 14 or 15 wherein the nitrogen containing gas further comprisesoxygen.

17. A method according to claim 16 where the nitrogen:oxygen ratio is between 1:99 and 99:1 wt:wt.

18. A method according to any one of claims 14 to 17 where the nitrogen containing gas is air.

19. A method according to any one of claims 14 to 18 wherein the plasma is generated by acombination of glow discharge and spark discharge or where the plasma is generated by pin discharge.

20. A method according to any one of claims 14 to 19 wherein the plasma-water or electrolyte water interface is at the interface of a bubble of gas in the water or electrolyte.

21. A method according to any one of claims 14 to 20 wherein the gaseous compound is provided at a relative humidity of 0-100%.22 A method according to any one of claims 14 to 21 wherein the water or electrolyte temperature is between 20 and 80°C.

23. A method according to any one of claims 14 to 21 wherein the electrolyte is aqueous H2SO4 or HCL24. A method according to any one of claims 14 to 21 wherein the electrolyte is aqueous KOH or NaOH.

25. A method according to any one of claims 14 to 21 wherein the electrolyte is aqueous KCI or NaCL26.     A method according to any one of claims 14 to 21 wherein the electrolyte is pure water.

27. A method according to any one of claims 14 to 21 wherein the dissolved NOX species are NO2or NOy.

28. A method according to any one of claims 14 to 21 wherein the dissolved NOX species are stored in a reservoir prior to catalytic reduction.

29. A method according to any one of the preceding claims wherein the electrocatalytic reduction is facilitated by a transition metal catalyst or transition metal oxide catalyst.

30. A method according to claim 29 wherein the transition metal is one or more of copper, nickel, iron, tin, bismuth, cobalt, titanium.

31. A method according to claim 29 wherein the transition metal catalyst is in the form of a foil, a foam, a nanostructured catalyst, a nanoparticulate catalyst or a single atom metal.

32. A method according to any one of claims 29 to 31 wherein the transition metal catalyst is located in the reaction system in a region adjacent the region of the spark discharge and / or glow discharge33. A method of reducing carbon containing gas comprising the steps of:subjecting the carbon containing gas to plasma forming conditions to form a carbon plasma;contacting the carbon plasma with water or an electrolyte at a plasma-water or electrolyte-water interface, thereby to provide a dissolved COX species; andelectrocatalytically reducing said COX species to provide one or more reduced compounds selected from CO, syngas or formate.

34. A method according to claim 33 wherein the carbon containing gas is i) an oxygen containing species or ii) further comprises O2.

35. A method according to claim 33 or claim 34 wherein the carbon containing gas is carbon dioxide.

36. Apparatus for reducing a gas comprising:i) a feed line to feed the gas to a glow / spark plasma discharge (pin-to-liquid with no enclosure, pin-to-liquid with nozzle enclosure, or a pin-to-liquid with a column bubbler enclosure) located at or below a liquid level in a reaction vessel;ii) the pin-to-liquid with no enclosure, pin-to-liquid with nozzle enclosure, ora pin-to-liquid with a column bubbler enclosure having a housing configured to generate bubbles in the liquid in a reaction vessel when in use; andiii) a feed line to transport dissolved plasma species from the reaction vessel to an electrocatalytic reduction chamber.

37. Apparatus for reducing a gas comprisingi) a feed line to feed the gas to a glow / spark plasma discharge (pin-to-liquid with no enclosure, pin-to-liquid with nozzle enclosure, or a pin-to-liquid with a column bubbler enclosure) located at or below a liquid level in a reaction vessel;ii) the pin-to-liquid with no enclosure, pin-to-liquid with nozzle enclosure, ora pin-to-liquid with a column bubbler enclosure having a housing configured to generate bubbles in the liquid in a reaction vessel when in use;iii) a fluid line to transport dissolved plasma reaction products from the reaction vessel to a reservoir; andiv) a feed line to transport dissolved plasma species from the reservoir to an electrocatalytic reduction chamber.

38. A catalyst comprising a transition metal catalyst in the form of a nanowire.

39. A catalyst according to claim 38 wherein the nanowire is supported on a transition metal foam.

40. A catalyst according to claim 38 or 39 wherein the catalyst is a copper nanowire supported bya copper foam.

41. A method according to any one of claims 1-35 wherein a metal oxide catalyst (either as nanoparticles or monolith) is packed inside the glow discharge region in plasma bubble column for enhancing generation rate of NOX species via synergistic plasma-catalyst interactions.

Images