Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum s...Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.展开更多
The percent ammonia nitrogen was determined in Passaic River waste water using Ion-Selective Electrode EPA Method 350.3. The intelligent ammonia sensor integrates ammonia electrode, pH electrode and Ammonia Ion electr...The percent ammonia nitrogen was determined in Passaic River waste water using Ion-Selective Electrode EPA Method 350.3. The intelligent ammonia sensor integrates ammonia electrode, pH electrode and Ammonia Ion electrode together to realize the in situ detection of ammonia. The test results have shown that the sensor is easy operation, low cost and no pollution. The ammonia is determined potentiometrically using an ammonia ion selective electrode and a pH/mV meter, having an expanded millivolt scale. The ammonia selective electrode uses a hydrophobic gas-permeable membrane to separate the sample solution from an electrode internal solution of ammonium chloride. Dissolved ammonia is converted to NH<sub>3</sub> gas by raising the pH to above 11.0 with a strong base. NH<sub>3</sub> gas diffuses the membrane and changes the internal solution pH that is sensed by the electrode. In single laboratory test results have been found 1.001 NH<sub>3</sub>-/L and 0.897 mg NH<sub>3</sub>-N/L, recoveries were 77.3% and 83.1%, respectively.展开更多
Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to i...Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems.展开更多
Carbon-free electrochemical nitrogen reduction reaction(NRR)is an appealing strategy for green ammonia synthesis,but there is still a significant performance bottleneck.Conventional working electrode is usually floode...Carbon-free electrochemical nitrogen reduction reaction(NRR)is an appealing strategy for green ammonia synthesis,but there is still a significant performance bottleneck.Conventional working electrode is usually flooded by the electrolyte during the NRR test,and only the surface material could get access to the nitrogen,which inevitably gives rise to sluggish reaction rate.Herein,an asymmetric electrode design is proposed to tackle this challenge.An aerophilic layer is constructed on one face of the electrocatalyst-loaded electrode,while the other side maintains its original structure,aiming to achieve facilitated nitrogen transfer and electrolyte permeation within the conductive skeleton simultaneously.This asymmetric architecture affords extensive threephase reaction region within the electrode as demonstrated by the combination of theoretical simulations and experimental measurements,which gives full play to the loaded electrocatalyst.As expected,the proofof-concept asymmetric electrode delivers an NH_(3)yield rate of 40.81μg h^(−1)mg^(−1)and a Faradaic efficiency of 71.71%at−0.3 V versus the reversible hydrogen electrode,which are more than 4 and 7 times that of conventional electrode,respectively.This work presents a versatile strategy for enhancing the interfacial reaction kinetics and is instructive to electrode design for gas-involved electrochemical reactions.展开更多
Electrolysis of ammonia in alkaline electrolyte solution was applied for the production of hydrogen. Both Pt-loaded Ni foam and Pt-Ir loaded Ni foam electrodes were prepared by electrodeposition and served as anode an...Electrolysis of ammonia in alkaline electrolyte solution was applied for the production of hydrogen. Both Pt-loaded Ni foam and Pt-Ir loaded Ni foam electrodes were prepared by electrodeposition and served as anode and cathode in ammonia electrolytic cell, respectively. The electrochemical behaviors of ammonia in KOH solution were individually investigated via cyclic voltammetry on three electrodes, i.e. bare Ni foam electrode, Pt-loaded Ni foam electrode and Pt-Ir loaded Ni foam electrode. The morphology and composition of the prepared Ni foam electrode were analyzed by scanning electron microscopy(SEM) and X-ray diffraction(XRD). Effects of the concentration of electrolyte solution and temperature of electrolytic cell on the electrolysis reaction were examined in order to enhance the efficiency of ammonia electrolysis. The competition of ammonia electrolysis and water electrolysis in the same alkaline solution was firstly proposed to explain the changes of cell voltage with the electrolysis proceeding. At varying current densities, different cell voltages could be obtained from galvanostatic curves.The low cell voltage of 0.58 V, which is less than the practical electrolysis voltage of water(1.6 V), can be obtained at a current density of2.5 mA/cm2. Based on some experimental parameters, such as the applied current, the resulting cell voltage and output of hydrogen gas, the power consumption per gram of H2produced can be estimated.展开更多
TiO2 nanotube （TINT） electrodes anodized in fluorinated organic solutions were successfully prepared on Ti sheets. Field-emission scanning electron microscopy （FE-SEM） and X-ray diffraction （XRD） were performed ...TiO2 nanotube （TINT） electrodes anodized in fluorinated organic solutions were successfully prepared on Ti sheets. Field-emission scanning electron microscopy （FE-SEM） and X-ray diffraction （XRD） were performed to characterize the TiNT electrodes. The linear voltammetry results under irradiation showed that the TiNT electrode annealed at 450℃ presented the highest photoelectrochemical activity. By combining photocatalytic with electrochemical process, a significantly synergetic effect on ammonia degradation was observed with Na2SO4 as supporting electrolyte at pH 10.7. Furthermore, the photoelectrocatalytic efficiency on the ammonia degradation was greatly enhanced in presence of chloride ions without the limitation ofpH. The degradation rate was improved by 14.8 times reaching 4.98 × 10^-2 min^-1 at pH 10.7 and a faster degradation rate of 6.34 × 10^-2 min^-1 was obtained at pH 3.01. The in situ photoelectrocatalytic generated active chlorine was proposed to be responsible for the improved efficiency. On the other hand, an enhanced degradation of ammonia using TiNT electrode fabricated in fluorinated organic solution was also confirmed compared to TiNT electrode anodized in fluorinated water solution and TiO2 film electrode fabricated by sol-gel method. Finally, the effect of chloride concentration was also discussed.展开更多
基金supported by is supported by the Shanghai Municipal Science and Technology Major Projectthe support from Shanghai Super Postdoctoral Incentive Program
文摘Focusing on revealing the origin of high ammonia yield rate on Cu via nitrate reduction(NO3RR),we herein applied constant potential method via grand-canonical density functional theory(GC-DFT)with implicit continuum solvation model to predict the reaction energetics of NO3RR on pure copper surface in alkaline media.The potential-dependent mechanism on the most prevailing Cu(111)and the minor(100)and(110)facets were established,in consideration of NO_(2)_(−),NO,NH_(3),NH_(2)OH,N_(2),and N_(2)O as the main products.The computational results show that the major Cu(111)is the ideal surface to produce ammonia with the highest onset potential at 0.06 V(until−0.37 V)and the highest optimal potential at−0.31 V for ammonia production without kinetic obstacles in activation energies at critical steps.For other minor facets,the secondary Cu(100)shows activity to ammonia from−0.03 to−0.54 V with the ideal potential at−0.50 V,which requires larger overpotential to overcome kinetic activation energy barriers.The least Cu(110)possesses the longest potential range for ammonia yield from−0.27 to−1.12 V due to the higher adsorption coverage of nitrate,but also with higher tendency to generate di-nitrogen species.Experimental evaluations on commercial Cu/C electrocatalyst validated the accuracy of our proposed mechanism.The most influential(111)surface with highest percentage in electrocatalyst determined the trend of ammonia production.In specific,the onset potential of ammonia production at 0.1 V and emergence of yield rate peak at−0.3 V in experiments precisely located in the predicted potentials on Cu(111).Four critical factors for the high ammonia yield and selectivity on Cu surface via NO3RR are summarized,including high NO3RR activity towards ammonia on the dominant Cu(111)facet,more possibilities to produce ammonia along different pathways on each facet,excellent ability for HER inhibition and suitable surface size to suppress di-nitrogen species formation at high nitrate coverage.Overall,our work provides comprehensive potential-dependent insights into the reaction details of NO3RR to ammonia,which can serve as references for the future development of NO3RR electrocatalysts,achieving higher activity and selectivity by maximizing these characteristics of copper-based materials.
文摘The percent ammonia nitrogen was determined in Passaic River waste water using Ion-Selective Electrode EPA Method 350.3. The intelligent ammonia sensor integrates ammonia electrode, pH electrode and Ammonia Ion electrode together to realize the in situ detection of ammonia. The test results have shown that the sensor is easy operation, low cost and no pollution. The ammonia is determined potentiometrically using an ammonia ion selective electrode and a pH/mV meter, having an expanded millivolt scale. The ammonia selective electrode uses a hydrophobic gas-permeable membrane to separate the sample solution from an electrode internal solution of ammonium chloride. Dissolved ammonia is converted to NH<sub>3</sub> gas by raising the pH to above 11.0 with a strong base. NH<sub>3</sub> gas diffuses the membrane and changes the internal solution pH that is sensed by the electrode. In single laboratory test results have been found 1.001 NH<sub>3</sub>-/L and 0.897 mg NH<sub>3</sub>-N/L, recoveries were 77.3% and 83.1%, respectively.
基金supported by the Climate Change Response Project (NRF-2019M1A2A2065612)the Brainlink Project (NRF2022H1D3A3A01081140)+3 种基金the NRF-2021R1A4A3027878 and the No. RS-2023-00212273 funded by the Ministry of Science and ICT of Korea via National Research Foundationresearch funds from Hanhwa Solutions Chemicals (1.220029.01)UNIST (1.190013.01)supported by the Institute for Basic Science (IBS-R019-D1)。
文摘Electrochemical N_(2) reduction reaction(eNRR) over Cu-based catalysts suffers from an intrinsically low activity of Cu for activation of stable N_(2) molecules and the limited supply of N_(2) to the catalyst due to its low solubility in aqueous electrolytes.Herein,we propose phosphorus-activated Cu electrocatalysts to generate electron-deficient Cu sites on the catalyst surface to promote the adsorption of N_(2) molecules.The eNRR system is further modified using a gas diffusion electrode(GDE) coated with polytetrafluoroethylene(PTFE) to form an effective three-phase boundary of liquid water-gas N_(2)-solid catalyst to facilitate easy access of N_(2) to the catalytic sites.As a result,the new catalyst in the flow-type cell records a Faradaic efficiency of 13.15% and an NH_(3) production rate of 7.69 μg h^(-1) cm^(-2) at-0.2 V_(RHE),which represent 3.56 and 59.2 times increases from those obtained with a pristine Cu electrode in a typical electrolytic cell.This work represents a successful demonstration of dual modification strategies;catalyst modification and N_(2) supplying system engineering,and the results would provide a useful platform for further developments of electrocatalysts and reaction systems.
基金National Natural Science Foundation of China,Grant/Award Numbers:U21A20332,52103226,52202275,52203314,12204253Distinguished Young Scholars Fund of Jiangsu Province,Grant/Award Number:BK20220061+1 种基金Fellowship of China Postdoctoral Science Foundation,Grant/Award Number:2021M702382Suzhou Foreign Academician Workstation,Grant/Award Number:SWY2022001。
文摘Carbon-free electrochemical nitrogen reduction reaction(NRR)is an appealing strategy for green ammonia synthesis,but there is still a significant performance bottleneck.Conventional working electrode is usually flooded by the electrolyte during the NRR test,and only the surface material could get access to the nitrogen,which inevitably gives rise to sluggish reaction rate.Herein,an asymmetric electrode design is proposed to tackle this challenge.An aerophilic layer is constructed on one face of the electrocatalyst-loaded electrode,while the other side maintains its original structure,aiming to achieve facilitated nitrogen transfer and electrolyte permeation within the conductive skeleton simultaneously.This asymmetric architecture affords extensive threephase reaction region within the electrode as demonstrated by the combination of theoretical simulations and experimental measurements,which gives full play to the loaded electrocatalyst.As expected,the proofof-concept asymmetric electrode delivers an NH_(3)yield rate of 40.81μg h^(−1)mg^(−1)and a Faradaic efficiency of 71.71%at−0.3 V versus the reversible hydrogen electrode,which are more than 4 and 7 times that of conventional electrode,respectively.This work presents a versatile strategy for enhancing the interfacial reaction kinetics and is instructive to electrode design for gas-involved electrochemical reactions.
基金supported by the National Natural Science Foundation of China(No.21103215)the Applied Basic Research Projects of Qingdao City(No.11-2-4-8-3-jch)
文摘Electrolysis of ammonia in alkaline electrolyte solution was applied for the production of hydrogen. Both Pt-loaded Ni foam and Pt-Ir loaded Ni foam electrodes were prepared by electrodeposition and served as anode and cathode in ammonia electrolytic cell, respectively. The electrochemical behaviors of ammonia in KOH solution were individually investigated via cyclic voltammetry on three electrodes, i.e. bare Ni foam electrode, Pt-loaded Ni foam electrode and Pt-Ir loaded Ni foam electrode. The morphology and composition of the prepared Ni foam electrode were analyzed by scanning electron microscopy(SEM) and X-ray diffraction(XRD). Effects of the concentration of electrolyte solution and temperature of electrolytic cell on the electrolysis reaction were examined in order to enhance the efficiency of ammonia electrolysis. The competition of ammonia electrolysis and water electrolysis in the same alkaline solution was firstly proposed to explain the changes of cell voltage with the electrolysis proceeding. At varying current densities, different cell voltages could be obtained from galvanostatic curves.The low cell voltage of 0.58 V, which is less than the practical electrolysis voltage of water(1.6 V), can be obtained at a current density of2.5 mA/cm2. Based on some experimental parameters, such as the applied current, the resulting cell voltage and output of hydrogen gas, the power consumption per gram of H2produced can be estimated.
基金supported by the National Natural Science Foundation of China (Nos. 21277134, 21107103)the State Key Laboratory of Environmental, Criteria and Risk Assessment Chinese Research Academy of Environmental Sciences
文摘TiO2 nanotube （TINT） electrodes anodized in fluorinated organic solutions were successfully prepared on Ti sheets. Field-emission scanning electron microscopy （FE-SEM） and X-ray diffraction （XRD） were performed to characterize the TiNT electrodes. The linear voltammetry results under irradiation showed that the TiNT electrode annealed at 450℃ presented the highest photoelectrochemical activity. By combining photocatalytic with electrochemical process, a significantly synergetic effect on ammonia degradation was observed with Na2SO4 as supporting electrolyte at pH 10.7. Furthermore, the photoelectrocatalytic efficiency on the ammonia degradation was greatly enhanced in presence of chloride ions without the limitation ofpH. The degradation rate was improved by 14.8 times reaching 4.98 × 10^-2 min^-1 at pH 10.7 and a faster degradation rate of 6.34 × 10^-2 min^-1 was obtained at pH 3.01. The in situ photoelectrocatalytic generated active chlorine was proposed to be responsible for the improved efficiency. On the other hand, an enhanced degradation of ammonia using TiNT electrode fabricated in fluorinated organic solution was also confirmed compared to TiNT electrode anodized in fluorinated water solution and TiO2 film electrode fabricated by sol-gel method. Finally, the effect of chloride concentration was also discussed.
