Recent progress in cathodic reduction-enabled organic electrosynthesis: Trends, challenges, and opportunities

Compared with general redox chemistry,electrochemistry using the electron as a potent,controllable,yet traceless alternative to chemical oxidants/reductants usually offers more sustainable options for achieving selective organic synthesis.With its environmentally benign features gradually being uncovered and studied,organic electrosynthesis is currently undergoing a revival and becoming a rapidly growing area within the synthetic community.Among the electrochemical transformations,the anodically enabled ones have been far more extensively exploited than those driven by cathodic reduction,although both approaches are conceptually attractive.To stimulate the development of cathodically enabled organic reactions,this review summarizes the recently developed reductive electrosynthetic protocols,discussing and highlighting reaction features,substrate scopes,applications,and plausible mechanisms to reveal the recent trends in this area.Herein,cathodic reduction-enabled preparative organic transformations are categorized into four types:reduction of(1)unsaturated hydrocarbons,(2)heteroatom-containing carbon-based unsaturated systems,(3)saturated C-hetero or C–C polar/strained bonds,and(4)hetero-hetero linkages.Apart from net electroreductive reactions,a few examples of reductive photo-electrosynthesis as well as paired electrolysis are also introduced,which offer opportunities to overcome certain limitations and improve synthetic versatility.The electrochemically driven,transition metal-catalyzed reductive cross-couplings that have been comprehensively discussed in several other recent reviews are not included here.

Electrochemical degradation of p-nitrophenol with different processes

The electrochemical degradation ofp-nitrophenol （PNP） under different conditions was investigated. The electrochemical behavior of PNP and its reduction product p-aminophenol （PAP） on stainless steel cathode and Ti/Pt anode through cyclic voltammetry were observed. Electrochemical degradation process was performed in an undivided cell and 92% PNP was removed corresponding to a 22% total organic carbon removal. A divided cell was also used and it was found that PNP degradation was mainly attributed to cathodic reduction, while anodic oxidation was responsible for PNP removal due to the reaction with hydroxyl radicals and surface oxide generated on the anode. The sequential electrolytic processes, reduction-oxidation and oxidation-reduction, were compared in the divided cell. In the case of reduction-oxidation process, the total organic carbon removal reached 40%, but PNP removal was the same with the undivided cell. A black deposit was found in the effluent and identified by Fourier transform infrared spectroscopy as a polymer of PAP produced by the 1,4-addition reaction of quinoneimine. Intermediates left in the solution such as hydroquinone, p-benzoquinone and PAP were determined by high performance liquid chromatography. Whereas, the oxidation-reduction process proved unsatisfying.

Effects of cathode potentials and nitrate concentrations on dissimilatory nitrate reductions by Pseudomonas alcaliphila in bioelectrochemical systems

The effects of cathode potentials and initial nitrate concentrations on nitrate reduction in bio- electrochemical systems （BESs） were reported. These factors could partition nitrate reduction between denitrification and dissimilatory nitrate reduction to ammonium （DNRA）. Pseudomonas alcaliphilastrain MBR utilized an electrode as the sole electron donor and nitrate as the sole electron acceptor. When the cathode potential was set from -0.3 to -I.1 V （vs. Ag/AgC1） at an initial nitrate concentration of 100 mg NO^-N/L, the DNRA electron recovery increased from （10.76 ± 1.6）% to （35.06 ± 0.99）%; the denitrification electron recovery decreased from （63.42 ± 1,32）% to （44.33 ± 1.92）%. When the initial nitrate concentration increased from （29.09 ± 0.24） to （490.97 ± 3.49） mg NO3-N/L at the same potential （-0.9 V）, denitrification electron recovery increased from （5.88 ± 1.08）% to （50.19 ±2.59）%; the DNRA electron recovery declined from （48.79 ±1.32）% to （16.02 ± 1.41）%. The prevalence of DNRA occurred at high ratios of electron donors to acceptors in the BESs and denitrification prevailed against DNRA under a lower ratio of electron donors to acceptors. These results had a potential application value of regulating the transformation of nitrate to N2 or ammonium in BESs for nitrate removal.