Single atom doping induced charge-specific distribution of Cu1-TiO_(2) for selective aniline oxidation via a new mechanism

Utilizing single atom sites doping into metal oxides to modulate their intrinsic active sites,achieving precise selectivity control in complex organic reactions,is a highly desirable yet challenging endeavor.Meanwhile,identifying the active site also represents a significant obstacle,primarily due to the intricate electronic environment of single atom site doped metal oxide.Herein,a single atom Cu doped TiO_(2)catalyst(Cu_(1)-TiO_(2)) is prepared via a simple“colloid-acid treatment”strategy,which switches aniline oxidation selectivity of TiO_(2) from azoxybenzene to nitrosobenzene,without using additives or changing solvent,while other metal or nonmetal doped TiO_(2) did not possess.Comprehensive mechanistic investigations and DFT calculations unveil that Ti-O active site is responsible for triggering the aniline to form a new PhNOH intermediate,two PhNOH condense to azoxybenzene over TiO_(2) catalyst.As for Cu_(1)-TiO_(2),the charge-specific distribution between the isolated Cu and TiO_(2) generates unique Cu_(1)-O-Ti hybridization structure with nine catalytic active sites,eight of them make PhNOH take place spontaneous dissociation to produce nitrosobenzene.This work not only unveils a new mechanistic pathway featuring the PhNOH intermediate in aniline oxidation for the first time but also presents a novel approach for constructing single-atom doped metal oxides and exploring their intricate active sites.

Metal-Free C_(3)N_(4) with plentiful nitrogen vacancy and increased specific surface area for electrocatalytic nitrogen reduction

As a substitute for synthetic ammonia under mild condition, electrocatalytic nitrogen reduction reaction(NRR) provides a hopeful approach for the development of ammonia. Nevertheless, the current development of NRR electrocatalysts is far from enough and a systematic research is needed to gain a better improvement. This article presents that 2 D C_(3)N_(4)-NV with a large specific surface area and abundant nitrogen vacancies is prepared by a simple and feasible method, and used as a metal-free catalyst for electrocatalytic NRR. Experiment result and density functional theory(DFT) calculation reveal that nitrogen vacancies in 2 D C_(3)N_(4)-NV can act as an efficient active site for catalytic NRR, which is conducive to capturing and activating N_(2), lowering Gibbs free energy(DG) in reaction and inhibiting hydrogen evolution reaction(HER) at the same time. In addition, the larger specific surface area also makes more active site exposed, which is good for the contact between the electrolyte and the active site, thus enhancing its NRR activity. The electrocatalyst shows an excellent catalytic activity for NRR in 0.1 M HCl, including Faradaic efficiency of 10.96%, NH_(3) yields of 17.85 lg h^(-1) mg_(cat)^(-1)., and good stability(over 20 h).

Nitrogen-doped carbon nanotubes by multistep pyrolysis process as a promising anode material for lithium ion hybrid capacitors

Lithium-ion hybrid capacitors(LIHCs) is a promising electrochemical energy storage devices which combines the advantages of lithium-ion batteries and capacitors.Herein,we developed a facile multistep pyrolysis method,prepared an amorphous structure and a high-level N-doping carbon nanotubes(NCNTs),and by removing the Co catalyst,opening the port of NCNTs,and using NCNTs as anode material.It is shows good performance due to the electrolyte ions enter into the electrode materials and facilitate the charge transfer.Furthermore,we employ the porous carbon material(APDC) as the cathode to couple with anodes of NCNTs,building a LIHCs,it shows a high energy density of 173 Wh/kg at 200 W/kg and still retains 53 Wh/kg at a high power density of 10 kW/kg within the voltage window of 0-4.0 V,as well as outstanding cyclic life keep 80% capacity after 5000 cycles.This work provides an opportunity for the preparation of NCNTs,that is as a promising high-performance anode for LIHCs.