Spatiotemporally modulated full-polarized light emission for multiplexed optical encryption.

Spatiotemporal control of full freedoms of polarized light emission is crucial in multiplexed optical computing, encryption and communication. Although recent advancements have been made in active emission or passive conversion of polarized light through solution-processed nanomaterials or metasurfaces, these design paths usually encounter limitations, such as small polarization degrees, low light utilization efficiency, limited polarization states, and lack of spatiotemporal control. Here, we addressed these challenges by integrating the spatiotemporal modulation of the LED device, the precise control and efficient polarization emission through nanomaterial assembly, and the programmable patterning/positioning using 3D printing. We achieved an extremely high degree of polarization for both linearly and circularly polarized emission from ultrathin inorganic nanowires and quantum nanorods thanks to the shear-force-induced alignment effect during the protruding of printing filaments. Real-time polarization modulation covering the entire Poincaré sphere can be conveniently obtained through the programming of the on-off state of each LED pixel. Further, the output polarization states can be encoded by an ordered chiral plasmonic film. Our device provides an excellent platform for multiplexing spatiotemporal polarization information, enabling visible light communication with an exceptionally elevated level of physical layer security and multifunctional encrypted displays that can encode both 2D and 3D information.

Ga-Modification Near-Surface Composition of Pt-Ga/C Catalyst Facilitates High-Efficiency Electrochemical Ethanol Oxidation through a C2 Intermediate.

In electrochemical ethanol oxidation reactions (EOR) catalyzed by Pt metal nanoparticles through a C2 route, the dissociation of the C-C bond in the ethanol molecule can be a limiting factor. Complete EOR processes producing CO2 were always exemplified by the oxidative dehydrogenation of C1 intermediates, a reaction route with less energy utilization efficiency. Here, we report a Pt3Ga/C electrocatalyst with a uniform distribution of Ga over the nanoparticle surface for EOR that produces CO2 at medium potentials (>0.3 V vs SCE) efficiently through direct and sustainable oxidation of C2 intermediate species, i.e., acetaldehyde. We demonstrate the excellent performance of the Pt3Ga-200/C catalyst by using electrochemical in situ Fourier transform infrared reflection spectroscopy (FTIR) and an isotopic labeling method. The atomic interval structure between Pt and Ga makes the surface of nanoparticles nonensembled, avoiding the formation of poisonous *CHx and *CO species via bridge-type adsorption of ethanol molecules. Meanwhile, the electron redistribution from Ga to Pt diminishes the *O/*OH adsorption and CO poisoning on Pt atoms, exposing more available sites for interaction with the C2 intermediates. Furthermore, the dissociation of H2O into *OH is facilitated by the high hydrophilicity of Ga, which is supported by DFT calculations, promoting the deep oxidation of C2 intermediates. Our work represents an extremely rare EOR process that produces CO2 without observing kinetic limitations under medium potential conditions.

Shaddock peels derived multilayer biochar with embedded CoO@Co nanoparticles for peroxymonosulfate based wastewater treatment.

The utilization of bio-wastes, such as shaddock peels, is of great significance for sustainable development. Combined with the potential of peroxymonosulfate (PMS) based advanced oxidation process (AOP) in wastewater treatment, a highly efficient functional catalyst, derived from shaddock peels biochar (SPC) and embedded with CoO@Co nanoparticles, i.e. Co-SPC-x(y), was prepared using a facile impregnation-calcination method and used for refractory organics degradation with PMS. The decoration amount of Co and annealing temperature were optimized, and the effects of various reaction factors were investigated. The results indicated that the optimized sample of Co-SPC-10 (900) consisted of multilayer biochar with curly edges and highly dispersed CoO@Co nanoparticles in the range of 20-200 nm, which is in cubic metallic Co and CoO. Moreover, it also possessed a specific surface area of 248.6 m2/g, and exhibited excellent PMS activation ability with ∼100% chlortetracycline hydrochloride (CTC) removal ratio within only 12 min of operation. The Co-SPC-10 (900)/PMS system showed relatively high tolerance for HPO42-, NO3- and SO42-, while the Cl- and HA had considerable effects on it. Mechanism exploration results revealed that both radical and non-radical pathways existed in the Co-SPC-10 (900)/PMS system, in which the multilayered biochar functioned as an electron transfer carrier to facilitate the continuous cycle of Co2+/Co3+ in the CoO@Co nanoparticles by reacting with the absorbed CTC and PMS, resulting in the production of •OH, SO4•-, O2•- and 1O2. Additionally, the Co-SPC-10 (900) also showed good stability and catalytic oxidation performance for various refractory organics.

Au-Pd nanoparticles immobilized on TiO2 nanosheet as an active and durable catalyst for solvent-free selective oxidation of benzyl alcohol.

TiO2nanocrystals with controlled facets have been extensively investigated due to their excellent photocatalytic performance in sustainable and green energy field. However, the applications in thermal catalysis without applying UV irradiation are comparably less and the identification of their intrinsic roles, especially the different catalytic behaviors of each crystal facet, remains not fully recognized. In this study, bimetallic AuPd nanoparticles supported on anatase TiO2 nanosheets exposing {001} facets or TiO2 nanospindles exposing {101} as a catalyst were prepared by sol-immobilization method and used for solvent-free benzyl alcohol oxidation. The experimental results indicated that the exposed facet of the support has a significant effect on the catalytic performance. AuPd/TiO2-001 catalyst exhibited a higher benzyl alcohol conversion than that of the AuPd/TiO2-101. Meanwhile, all the prepared AuPd/TiO2 catalysts were characterized by XRD, ICP-AES, XPS, BET, TEM, and HRTEM. The results revealed that the higher number of oxygen vacancies in TiO2-sheets with the exposed {001} facets of higher surface energy could be responsible for the observed enhancement in the catalytic performance of benzyl alcohol oxidation. The present study displays that it is plausible to enhance the catalytic performance for the benzyl alcohol oxidation by tailoring the exposed facet of the TiO2 as a catalyst support.

Ab initio study on anomalous structures of anionic [(N-heterocycle)-CO2]- complexes.

Several unusual anionic complexes between carbon dioxide (CO2) and N-heterocycles (NHCs) possessing a significantly positive adiabatic electron affinity over 0.7 eV were studied by density functional theory calculations (UB3LYP/6-311++g(d,p)). Unlike all previously reported [NHC-CO2]- anions with a coplanar structure that ensures full delocalization of the negative charge through extended π-conjugation, this new class of anionic [NHC-CO2]- complexes has a strongly non-coplanar geometry and no π-bond character between CO2 and NHC. Despite the fundamental differences in chemical bonding between all prior cases and the new class of [NHC-CO2]- complexes, we found that the CO2 moiety in the latter still has a large negative charge (∼0.4 e) and a strongly bent geometry (O-C-O angle of ∼140°) just like in the former. This seemingly anomalous case was explained by a simple model based on the torsional steric effect and the electron affinities of the constituent moieties.