The j–pH diagram of interfacial reactions involving H+ and OH-

For aqueous interfacial reactions involving H+and OH-, the interfacial pH varies dynamically during the reaction process, which is a key factor determining the reaction performance. Herein, the kinetic relevance between the interfacial pH and reaction rate is deciphered owing to the success in establishing the transport equations of H+/OH- in unbuffered solutions, and is charted as a current(j)–pH diagram in the form of an electrochemical response. The as-described j–pH interplay is experimentally verified by the oxygen reduction and hydrogen evolution reactions. This diagram serves to form a panoramic graphic view of pH function working on the interfacial reactions in conjunction with the Pourbaix’s potential–pH diagram, and particularly enables a kinetic understanding of the transport effect of H+and OH-on the reaction rate and valuable instruction toward associated pH control and buffering manipulation.

Efficient electroreduction of nitrate via enriched active phases on copper-cobalt oxides

Electrochemical conversion of nitrate(NO_(3)~-) to ammonia(NH_(3)) can target two birds with one stone well, in NO_(3)^(-)-containing sewage remediation and sustainable NH_(3) production. However, single metalbased catalysts are difficult to drive high-efficient NO_(3)~- removal due to the multi-electron transfer steps.Herein, we present a tandem catalyst with simple structure, Cu-Co binary metal oxides(Cu-Co-O), by engineering intermediate phases as catalytic active species for NO_(3)~- conversion. Electrochemical evaluation,X-ray photoelectron spectroscopy, and in situ Raman spectra together suggest that the newly-generated Cu-based phases was prone to NO_(3)~- to NO_(2)~- conversion, then NO_(2)~- was reduced to NH_(3) on Co-based species. At an applied potential of -1.1 V vs. saturated calomel electrode, the Cu-Co-O catalyst achieved NO_(3)~- -N removal of 90% and NH_(3) faradaic efficiency of 81% for 120 min in 100 m L of 50 mg/L NO_(3)~- -N,consuming only 0.69 k Wh/mol in a two-electrode system. This study provides a facile and efficient engineering strategy for developing high-performance catalysts for electrocatalytic nitrate conversion.

Derivative-extremum analysis of current-potential curves showing electrochemical kinetics in the full reversibility range

Derivative-extremum analysis(DEA) of j-E curves is a newly proposed method of half wave potential(E1/2) and activation feature extraction from steady-state voltammetry. Here, the DEA is demonstrated to be valid in the full range of reversibility using numerical simulations with a derived universal electrode equation, providing a novel perspective of electrochemical kinetics in the reversibility domain. The results reveal that E1/2is a better choice of the reference potential instead of equilibrium potential(Eeq) in electrode equations, especially since Eeqis meaningless in an irreversible case. The equations referenced with standard potential, E1/2and Eeq, are summarized in three tables, and their applications in parameter determinations are specified. Finally, reversibility is proved to be a relative measure between kinetic slowness and mass transport of electroactive species, and the reversibility classifications are proposed according to the DEA feature in the reversibility domain. This work, based on the DEA principle, refines the electrode equation forms and generalizes their applicability in the full range of reversibility.

Enhancing sensitivity of microbial fuel cell sensors for low concentration biodegradable organic matter detection:Regulation of substrate concentration,anode area and external resistance

The relatively low sensitivity is an important reason for restricting the microbial fuel cell(MFC)sensors'application in low concentration biodegradable organic matter(BOM)detection.The startup parameters,including substrate concentration,anode area and external resistance,were regulated to enhance the sensitivity of MFC sensors.The results demonstrated that both the substrate concentration and anode area were positively correlated with the sensitivity of MFC sensors,and an external resistance of 210Ωwas found to be optimal in terms of sensitivity of MFC sensors.Optimized MFC sensors had lower detection limit(1 mg/L)and higher sensitivity(Slope value of the linear regression curve was 1.02),which effectively overcome the limitation of low concentration BOM detection.The essential reason is that optimized MFC sensors had higher coulombic efficiency,which was beneficial to improve the sensitivity of MFC sensors.The main impact of the substrate concentration and anode area was to regulate the proportion between electrogens and nonelectrogens,biomass and living cells of the anode biofilm.The external resistance mainly affected the morphology structure and the proportion of living cells of the anode.This study demonstrated an effective way to improve the sensitivity of MFC sensors for low concentration BOM detection.

pH Overpotential for Unveiling the pH Gradient Effect of H^(+)/OH^(−)Transport in Electrode Reaction Kinetics

The pH gradient caused by H^(+)/OH^(−)transport on an electrode surface is the key factor determining reaction performance,but its detailed impact on the electrode reaction kinetics has yet to be clarified.Here,the pH gradient effect was determined by developing electrode reaction equations,considering the overpotential assigned to the pH gradient called pH overpotential.The pH gradient effect was revealed to involve two aspects:(1)the Nernst pH overpotential,accounting for the common Nernst relationship with pH,and(2)the pH-dependent function of the electron-transfer coefficient(α_(pH)).Both parts were verified experimentally using oxygen reduction reaction and hydrogen evolution reaction,obviously,with differentα_(pH) functions.Detailedα_(pH) function effect was clarified based on numerical calculations of the electrode reaction equations.We found that the effect could be assessed suitably by an apparent constant(α_(app))and a nonlinear fitting method proposed forα_(app) value estimation.The results of this study provide the kinetic fundamentals of electrode reactions involving H^(+)/OH^(−)and contribute to the understanding and assessment of their performance with the H^(+)/OH^(−)transport effect.