Efficient nitrogen fixation through a reactive plasma process attracts intense interest due to the environmental issues induced by the conventional Haber–Bosch method. In this work, we present a direct and simple fix...Efficient nitrogen fixation through a reactive plasma process attracts intense interest due to the environmental issues induced by the conventional Haber–Bosch method. In this work, we present a direct and simple fixation routine without any catalysts for nitrogen in open air using an atmospheric-pressure pin-to-solution plasma electrolytic system. Nitrate, nitrite, and ammonia as the nitrogen-derived chemicals in solution were analyzed as indicators under various discharge conditions to estimate the energy efficiency of this process. The results show that the nitrogen fixation process was much more efficient by the pin-positive discharge compared to the negative one. N chemicals preferred to be formed when the solution was of negative polarity. It was also found that, with the help of solution circulation, the energy efficiency was enhanced compared to that of static liquid. However, an inverse trend was observed with the increase of the discharge current. Further study by optical emission spectroscopy indicates the important roles of active N2* and water vapour and their derived species near the plasma–water interface in the fixation process.展开更多
Nitric oxide(NO)is one of the most crucial products in the plasma-based nitrogen fixation process.In this work,in situ measurements were performed for quantifying the NO synthesis spatially in a warm air glow discharg...Nitric oxide(NO)is one of the most crucial products in the plasma-based nitrogen fixation process.In this work,in situ measurements were performed for quantifying the NO synthesis spatially in a warm air glow discharge,through the method of Mid-infrared quantum cascade laser absorption spectroscopy(QCL-AS).Two ro-vibrational transitions at 1900.076 cm^(-1) and 1900.517 cm^(-1) of the ground-state NO(X)were probed sensitively by the help of the wavelength modulation spectroscopy(WMS)approach to increase the signal/noise(S/N)level.The results show a decline trend of NO synthesis rate along the discharge channel from the cathode to the anode.However,from the point of energy efficiency,the cathode region is of significantly low energy efficiency of NO production.Severe disproportionality was found for the high energy consumption but low NO production in the region of cathode area,compared to that in the positive column zone.Further analysis demonstrates the high energy cost of NO production in the cathode region,is ascribed to the extremely high reduced electric field E/N therein not selectively preferable for the processes of vibrational excitation or dissociation of N_(2) and O_(2) molecules.This drags down the overall energy efficiency of NO synthesis by this typical warm air glow discharge,particularly for the ones with short electrode gaps.Limitations of further improving the energy cost of NO synthesis by variations of the discharge operation conditions,such as discharge current or airflow rate,imply other effective manners able to tune the energy delivery selectively to the NO formation process,are sorely needed.展开更多
基金partly supported by National Natural Science Foundation of China (No. 11975061)the Technology Innovation and Application Development Project of Chongqing (No. cstc2019jscx-msxmX0041)+1 种基金the Construction Committee Project of Chongqing (No. 2018-1-3-6)the Fundamental Research Funds for the Central Universities (No. 2019CDQYDQ034)。
文摘Efficient nitrogen fixation through a reactive plasma process attracts intense interest due to the environmental issues induced by the conventional Haber–Bosch method. In this work, we present a direct and simple fixation routine without any catalysts for nitrogen in open air using an atmospheric-pressure pin-to-solution plasma electrolytic system. Nitrate, nitrite, and ammonia as the nitrogen-derived chemicals in solution were analyzed as indicators under various discharge conditions to estimate the energy efficiency of this process. The results show that the nitrogen fixation process was much more efficient by the pin-positive discharge compared to the negative one. N chemicals preferred to be formed when the solution was of negative polarity. It was also found that, with the help of solution circulation, the energy efficiency was enhanced compared to that of static liquid. However, an inverse trend was observed with the increase of the discharge current. Further study by optical emission spectroscopy indicates the important roles of active N2* and water vapour and their derived species near the plasma–water interface in the fixation process.
基金partly supported by National Natural Science Foundation of China(Nos.11975061,52111530088)the Technology Innovation and Application Development Project of Chongqing(No.cstc2019jscx-msxm X0041)+1 种基金the Construction Committee Project of Chongqing(No.2018-1-3-6)the Fundamental Research Funds for the Central Universities(No.2019CDQYDQ034)。
文摘Nitric oxide(NO)is one of the most crucial products in the plasma-based nitrogen fixation process.In this work,in situ measurements were performed for quantifying the NO synthesis spatially in a warm air glow discharge,through the method of Mid-infrared quantum cascade laser absorption spectroscopy(QCL-AS).Two ro-vibrational transitions at 1900.076 cm^(-1) and 1900.517 cm^(-1) of the ground-state NO(X)were probed sensitively by the help of the wavelength modulation spectroscopy(WMS)approach to increase the signal/noise(S/N)level.The results show a decline trend of NO synthesis rate along the discharge channel from the cathode to the anode.However,from the point of energy efficiency,the cathode region is of significantly low energy efficiency of NO production.Severe disproportionality was found for the high energy consumption but low NO production in the region of cathode area,compared to that in the positive column zone.Further analysis demonstrates the high energy cost of NO production in the cathode region,is ascribed to the extremely high reduced electric field E/N therein not selectively preferable for the processes of vibrational excitation or dissociation of N_(2) and O_(2) molecules.This drags down the overall energy efficiency of NO synthesis by this typical warm air glow discharge,particularly for the ones with short electrode gaps.Limitations of further improving the energy cost of NO synthesis by variations of the discharge operation conditions,such as discharge current or airflow rate,imply other effective manners able to tune the energy delivery selectively to the NO formation process,are sorely needed.