Single-Molecule Confinement Induced Intrinsic Multi-Electron Redox-Activity to Enhance Supercapacitor Performance

Aggregation of polyoxometalates(POM)is largely responsible for the reduced performance of POM-based energy-storage systems.To address this challenge,here,the precise confinement of single Keggin-type POM molecule in a porous carbon(PC)of unimodal super-micropore(micro-PC)is realized.Such precise single-molecule confinement enables sufficient activity center exposure and maximum electron-transfer from micro-PC to POM,which well stabilizes the electron-accepting molecules and thoroughly activates its inherent multi-electron redox-activity.In particular,the redox-activities and electron-accepting properties of the confined POM molecule are revealed to be super-micropore pore size-dependent by experiment and spectroscopy as well as theoretical calculation.Meanwhile,the molecularly dispersed POM molecules confined steadily in the“cage”of micro-PC exhibit unprecedented large-negative-potential stability and multiple-peak redox-activity at an ultra-low loading of~11.4 wt%.As a result,the fabricated solid-state supercapacitor achieves a remarkable areal capacitance,ultrahigh energy and power density of 443 mF cm^(-2),0.12 mWh cm^(-2)and 21.1 mW cm^(-2),respectively.This work establishes a novel strategy for the precise confinement of single POM molecule,providing a versatile approach to inducing the intrinsic activity of POMs for advanced energy-storage systems.

Realization of solid-state red fluorescence and concentration-induced multicolor emission from N,B co-doped carbon dots

As a new type of luminescent material,carbon dots(CDs)have attracted increased attention for their superior optical properties in recent years.However,solidstate fluorescent CDs,especially with red emission,are still a major challenge.Here,CDs with solid-state red emission were synthesized by co-doping of N and B using the one-step microwave method.The CD powder exhibits excitation-independent solid-state red fluorescence without any dispersion matrices,with optimum solid-state fluorescence wavelength of 623 nm.The hydrogen bonding interaction in CDs is helpful for solid-state fluorescence of CDs.The IG/ID value of CDs reaches up to 3.49,suggesting their very high graphitization degree,which is responsible for their red emission.In addition,CDs show the concentration-induced multicolor emission,which is attributed to the decreased energy gap in the high concentrated CD solution.To exploit their concentration-dependent emission,CDs with changing ratio in matrices are applied as a color-converting layer on ultraviolet chip to fabricate multicolor light-emitting diodes with light coordinates of(0.33,0.38),(0.41,0.48),(0.49,0.44),and(0.67,0.33),which belong to green,yellow,orange,and red light,respectively.