Construction of phosphorus-doping with spontaneously developed selenium vacancies: Inducing superior ion-diffusion kinetics in hollow Cu_(2)Se@C nanospheres for efficient sodium storage

Achieving high-efficiency sodium storage in metal selenides is still severely constrained in consideration of their inferior electronic conductivity and inadequate Na^(+)insertion pathways and active sites.Heteroatom doping accompanied by spontaneously developed lattice defects can effectively tune electronic structure of metal selenides,which give a strong effect to motivate fast charge transfer and Na^(+)accessibility.Herein,we finely designed and successfully constructed a fascinating phosphorus-doped Cu_(2)Se@C hollow nanosphere with abundant vacancy defects(Cu_(2)P_(x)Se_(1-x)@C)through a combination strategy of selenization of Cu_(2)O nanosphere template,self-polymerization of dopamine,and subsequent phosphorization treatment.Such exquisite composite possesses enriched active sites,superior conductivity,and sufficient Na^(+)insertion channel,which enable much faster Na^(+)diffusion rates and more remarkable pseudocapacitive features,Satisfyingly,the Cu_(2)P_(x)Se_(1-x)@C composites manifest the supernormal sodium-storage capabilities,that is,a reversible capacity of 403.7 mA h g^(-1) at 1.0 A g^(-1) over 100 cycles,and an ultrastable cyclic lifespan over 1000 cycles at 20.0 A g^(-1) with a high capacity-retention of about249.7 mA h g^(-1).The phase transformation of the Cu_(2)P_(x)Se_(1-x)@C involving the intercalation of Na^(+)into Cu_(2)Se and the following conversion of NaCuSe to Cu and Na2Se were further demonstrated through a series of ex-situ characterization methods.DFT results demonstrate that the coexistence of phosphorusdoping and vacancy defects within Cu_(2)Se results in the reduction of Na^(+)adsorption energy from-1.47to-1.56 eV improving the conductivity of Cu_(2)Se to further accelerate fast Na^(+)mobility.

Sulfation of the extracellular polysaccharide from the edible fungus Stropharia rugosoannulata with its antioxidant activity

An acidic extracellular polysaccharide(EPS)was gained from Stropharia rugosoannulata fermentation broth by the alcohol precipitate method.Sulfated derivative of EPS(S-EPS)was gained by chlorosulfonic acid-pyridine method and the conditions were as follows:pyridine as the reaction solvent,temperature 80°C,and reaction time 90 min.The chemical structure and chain conformation of EPS and S-EPS were characterized by FT-IR,NMR and size exclusion chromatography(SEC)coupled with multi-angle laser light scattering(MALLS)detection.FT-IR spectra indicated the sulfated group was linked to the polymer.The EPS mainly consists of mannose,glucose and glucuronic acid,and the glycosidic bond type is mainly(1→4)-linked and(1→6)-linked.C6 and C2 were substituted by sulfate groups.The EPS was degraded into smaller molecular weight(Mw)polysaccharides with the larger molecular size(Rg)after sulfation and S-EPS has better hydrophilicity.Moreover,the sulfated derivative S-EPS was found to have a better scavenging ability on hydroxyl radicals than EPS.It proved that the chemical modification of S.rugosoannulata polysaccharides by sulfation effectively enhanced their antioxidant activity.