ABSTRACT
Defect engineering can provide a feasible approach to achieving ambient molecular oxygen activation. However, conventional surface defects (e.g., oxygen vacancies, OVs), featured with the coordinatively unsaturated metal sites, often favor the reduction of O2 to â¢O2- rather than O22- via two-electron transfer, hindering the efficient pollutant removal with high electron utilization. Herein, we demonstrate that this bottleneck can be well discharged by modulating the electronic structure of OVs via phosphorization. As a proof of concept, TiO2 nanoparticles are adopted as a model material for NaH2PO2 (HP) modification, in which HP induces the formation of OVs via weakening the Ti-O bonds through the hydrogen bond interactions. Additionally, the formed Ti-O-P covalent bond refines the electronic structure of OVs, which enables rapid electron transfer for two-electron molecular oxygen activation. As exemplified by NO oxidation, HP-modified TiO2 with abundant OVs achieved complete NO removal with high selectivity for benign nitrate, superior to that of pristine TiO2. This study highlights a promising approach to regulate the O2 activation via an electronic structure modulation and provides fresh insights into the rational design of a photocatalyst for environmental remediation.
Subject(s)
Electrons , Oxygen , Hydrogen Bonding , Oxidation-ReductionABSTRACT
The selective conversion of dilute NO pollutant into low-toxic product and simultaneous storage of metabolic nitrogen for crop plants remains a great challenge from the perspective of waste management and sustainable chemistry. This study demonstrates that this bottleneck can be well tackled by refining the reactive oxygen species (ROS) on Ni-modified NH2 -UiO-66(Zr) (Ni@NU) using nickel foam (NF) as a three-dimensional (3D) substrate through a flow photoanode reactor via the gas-phase photoelectrocatalysis. By rationally refining the ROS to â OH, Ni@NU/NF can rapidly eliminate 82 % of NO without releasing remarkable NO2 under a low bias voltage (0.3â V) and visible light irradiation. The abundant mesoporous pores on Ni@NU/NF are conducive to the diffusion and storage of the formed nitrate, which enables the progressive conversion NO into nitrate with selectivity over 99 % for long-term use. Through calculation, 90 % of NO could be recovered as the nitrate species, indicating that this state-of-the-art strategy can capture, enrich and recycle the pollutant N source from the atmosphere. This study offers a new perspective of NO pollutant treatment and sustainable nitrogen exploitation, which may possess great potential to the development of highly efficient air purification systems for industrial and indoor NOx control.
ABSTRACT
Five-layer antireflective coating for the visible and the infrared has been successfully fabricated by a solgel route on quartz substrate. The quarter-half-quarter multilayer structure with two buffer layers is optimized by the optical admittance approach. Mesoporous SiO2 film templated by an ethylene oxide-propylene oxide-ethylene oxide triblock copolymer is used as the top layer, and SiO2-TiO2 hybrid films are employed as the other layers. The grazing incidence small-angle x-ray scattering results indicate the ordered mesopores in the low-index SiO2 film, as well as the homogeneity of the SiO2-TiO2 hybrid films. Transmittance spectra are fitted to obtain film thicknesses and refractive indices, providing the main technological parameters for theory designs. A short heat-treatment step followed by a shock cooling process is introduced to suppress crack formation in film stacks. The transmittance of the obtained five-layer antireflective coating exceeds 99% at 500-700 nm, and the maximum value in the infrared region is 97.84% at 1100 nm. This work is a beneficial attempt to fabricate antireflective coatings with multilayer structure through the soft solgel route.
ABSTRACT
A new antireflective silica film with closed mesopores was successfully prepared for the optical elements used in vacuum of a high-power laser system. The ordered cagelike mesopores were formed with the direction of surfactant F127 and then closed by long-chain fluoroalkylsilane. The grazing incident x-ray diffraction and grazing incident small-angle x-ray scattering results indicated that the mesopores in film constructed a body-center cubic structure. The films exhibited excellent transmittance as high as 99.98% on quartz substrate. After a 1-month antipollution test with polydimethylsiloxane in vacuum, the decrease of transmittance was small as 0.02%. This film had a high laser-induced damage threshold of above 28 J/cm(2) at 1 ns laser pulse of 1053 nm wavelength.
ABSTRACT
Transmission measurements have been used to investigate the optical properties of polyvinylpyrrolidone (PVP)/ZrO(2) films synthesized by the solgel route. The optical constants of PVP/ZrO(2) films deposited on quartz substrates were determined by fitting transmission spectra in the wavelength range of 200-800 nm with the Tauc-Lorentz and Cody-Lorentz physical models. Combined with Urbach tail, both models give a good description of transmission data and reveal that refractive index of film slightly decreases with increasing PVP mass fraction. X-ray reflectivity (XRR) measurements were also performed on PVP/ZrO(2) films to complement the thicknesses. The value of film thickness, including interface information from transmission spectra, is consistent with that result obtained from XRR, indicating that fitting transmission spectrum is a high reliable optical characterization.
