Strategic regulation of nitrogen-containing intermediates for enhanced nitrate reduction over Co_(3)O_(4)/SiC catalyst having multiple active centers

Regulating the intermediates involved in the electrocatalytic nitrate reduction reaction(NO_(3)RR)is crucial for the enhancement of reaction efficiency.However,it remains a great challenge to regulate the reaction intermediates through active site manipulation on the surface of the catalyst.Here,a family of n%-Co_(3)O_(4)/SiC(n=5,8,12,20)catalysts with a delicate percentage of Co^(2+)and Co^(3+)were prepared for NO_(3)RR.We found that Co^(3+)primarily acts as the active site for NO_(3)^(−)reduction to NO_(2)^(−),while Co^(2+)is responsible for the conversion of NO_(2)^(−)to NH_(3).Moreover,the conversion of these intermediates over the active sites is autonomous and separately controllable.Both processes synergistically accomplish the reduction of nitrate ions to synthesize ammonia.Combining the experimental studies and density functional theory(DFT)calculations,it is discovered the pathway(^(*)NHO→^(*)NHOH→^(*)NH_(2)OH→^(*)NH_(2)→^(*)NH_(3))is more favorable due to the lowerΔG value(0.25 eV)for the rate-limiting step(^(*)NO→^(*)NHO).The NH_(3)yield rate of 8%-Co_(3)O_(4)/SiC reached 1.08 mmol/(cm^(2)h)with a Faradaic efficiency of 96.4%at−0.89 V versus the reversible hydrogen electrode(RHE),surpassing those of most reported non-noble NO_(3)RR catalysts.This strategy not only provides an efficient catalyst for NO_(3)RR but also serves as an illustrative model for the regulation of multi-step reaction intermediates through the design of distinct active sites,thereby presenting a new approach to enhance the efficiency of intricate reactions.

A Backstepping Simple Adaptive Control Application to Flexible Space Structures

Although the simple adaptive control （SAC） is widely studied both in theory and application in flexible space structure control and other control problems, it is restricted by the almost strictly positive real （ASPR） conditions. In most practical control problems, the ASPR conditions are not satisfied. Therefore, based on the SAC theory, this paper proposes a backstepping simple adaptive control algorithm which suits the system with arbitrary relative degree with no need of parallel feed forward compensa- tor. The proposed control algorithm consists of decomposition of the arbitrary relative degree system into a known subsystem and an unknown ASPR subsystem which are connected in cascade, design of constant output feedback controller for the known subsystem, and implementation of backstepping method and SAC of the unknown ASPR subsystem. Inheriting the characteristics of the SAC, this method can be adaptive online for the parameter uncertainties. Then, the application of the proposed controller to large flexible space structure with collocated sensors and actuators is studied, and the simulation results validate the proposed controller. It is a new strategy to apply the classical SAC to high relative degree plants.