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.

Successful Nitrogen Doping of 1.3 GHz Single Cell Superconducting Radio-Frequency Cavities

A high intrinsic quality factor （Q0） of a superconducting radio-frequency cavity is beneficial to reducing the oper- ation costs of superconducting accelerators. Nitrogen doping （N-doping） has been demonstrated as a aseful way to improve Q0 of the superconducting cavity in recent years. N-doping researches with 1.3 GHz single cell cavities are carried out at Peking University and the preliminary results are promising. Our recipe is slightly different from other laboratories. After 250μm polishing, high pressure rinsing and 3 h high temperature annealing, the cavities are nitrogen doped at 2.7-4.0Pa for 20rain and then followed by 15μm electropolishing. Vertical test results show that Q0 of a 1.3 GHz single cell cavity made of large grain niobium has increased to 4 ×10 10 at 2.0K and medium gradient.

Preparation and Gas-sensing Characteristics of Na^+-doped ZnO Single Crystals

ZnO single crystals were grown by vapor phase reaction of Zno powder with active carbon powdei at an elevated temperature The typical crystals were colorless and transparent with maximum size o4 0.1 mm in diameter and 25 mm in length, The gas-sensing characteristics of Na+-doped anc undoped single crystals were investigated in 1 %H2. Co and CH, in air between 1 50 and 600℃. It was found that the undoped ZnO single crystals showed little gas sensitivity in air. and Na+-doping can greatly enhance the senstivity by increasing the resistivities. The maximum sensitivity of the samples is 22 (Ra/ Rg) for H2. 1 2 for CO and 4 for CH4

High-throughput calculation-based rational design of Fe-doped MoS_(2) nanosheets for electrocatalytic p H-universal overall water splitting

Electrocatalytic water splitting is crucial for H2generation via hydrogen evolution reaction(HER)but subject to the sluggish dynamics of oxygen evolution reaction(OER).In this work,single Fe atomdoped MoS_(2)nanosheets(SFe-DMNs)were prepared based on the high-throughput density functional theory(DFT)calculation screening.Due to the synergistic effect between Fe atom and MoS_(2)and optimized intermediate binding energy,the SFe-DMNs could deliver outstanding activity for both HER and OER.When assembled into a two-electrode electrolytic cell,the SFe-DMNs could achieve the current density of 50 mA cm^(-2)at a low cell voltage of 1.55 V under neutral condition.These results not only confirmed the effectiveness of high-throughput screening,but also revealed the excellent activity and thus the potential applications in fuel cells of SFe-DMNs.

A cascade of in situ conversion of bicarbonate to CO_(2) and CO_(2) electroreduction in a flow cell with a Ni-N-S catalyst

Combination of CO_(2) capture using inorganic alkali with subsequently electrochemical conversion of the resultant HCO_(3)^(-)to high-value chemicals is a promising route of low cost and high efficiency.The electrochemical reduction of HCO_(3)^(-)is challenging due to the inaccessible of negatively charged molecular groups to the electrode surface.Herein,we adopt a comprehensive strategy to tackle this challenge,i.e.,cascade of in situ chemical conversion of HCO_(3)^(-)to CO_(2) and CO_(2) electrochemical reduction in a flow cell.With a tailored Ni-N-S single atom catalyst(SACs),where sulfur(S)atoms located in the second shell of Ni center,the CO_(2)electroreduction(CO_(2)ER)to CO is boosted.The experimental results and density functional theory(DFT)calculations reveal that the introduction of S increases the p electron density of N atoms near Ni atom,thereby stabilizing^(*)H over N and boosting the first proton coupled electron transfer process of CO_(2)ER,i.e.,^(*)+e^(-)+^(*)H+^(*)CO_(2)→^(*)COOH.As a result,the obtained catalyst exhibits a high faradaic efficiency(FE_(CO)~98%)and a low overpotential of 425 mV for CO production as well as a superior turnover frequency(TOF)of 47397 h^(-1),outcompeting most of the reported Ni SACs.More importantly,an extremely high FECOof 90%is achieved at 50 mA cm^(-2)in the designed membrane electrode assembly(MEA)cascade electrolyzer fed with liquid bicarbonate.This work not only highlights the significant role of the second coordination on the first coordination shell of the central metal for CO_(2)ER,but also provides an alternative and feasible strategy to realize the electrochemical conversion of HCO_(3)^(-)to high-value chemicals.

Influence of Metallic Substitutions on the Optical and Mechanical Properties of NLO Benzoyl Glycine Crystals

Benzoyl glycine （BG） is a promising organic nonlinear optical （NLO） crystal, whose second harmonic generation （SHG） efficiency is much higher than that of KDP （potassium dihydrogen phosphate）. Single crystals of pure, Cu2＋ and Cd2＋ doped BG were grown by slow evaporation technique. Optically transparent and defect free single crystals of size up to 10 mm×15 mm×10 mm were harvested in a period of 40-60 days. The growth conditions of pure and doped crystals of BG were optimized and the grown crystals were confirmed by single crystal XRD （X-ray diffraction）. The grown crystals were characterized by FTIR （Fourier transform infrared spectroscopy）, optical absorption and microhardness studies. The microhardness studies confirm that BG has a moderate VHN （Vickers hardness number） value in comparison to the.other organic NLO crystals. The efficiency of frequency doubling was measured for the using Nd：YAG laser and the results were discussed.

Tm^(3+) and Nd^(3+) singly doped LiYF_4 single crystals with 3-5 μm mid-infrared luminescence

Mid-infrared（MIR） emissions of 2.4 and 3.5 μm from Tm3＋：LiYF4 single crystals attributed to3H4 →3H5 and3H5 →3F4 transitions as well as MIR emissions of 4.2,4.3,and 4.5 μm from Nd3＋：LiYF4 lasers attributed to4I15/2 →4I13/2,4I13/2 →4I11/2,and4I11/2 →4I9/2 transitions,respectively,are observed.LiYF4 single crystals possess high transmittance of over 85% in the 2.5-6 μm range.The large emission crosssections of Tm-doped crystals at 2.4 μm（1.9×10-20cm2） and Nd-doped crystals at 4.2 μm（0.84×10-20 cm2） as well as the high rare-earth doping concentrations,excellent optical transmission,and chemicalphysical properties of the resultant samples indicate that Nd3＋and Tm3＋singly doped crystals may be promising materials for application in MIR lasers.

Crystal characterization and optical spectroscopy of Eu^(3+)-doped CaGdAlO_4 single crystal fabricated by the floating zone method

A highly transparent Eu3＋-doped CaGdA104 （CGA） single crystal is grown by the floating zone method. The segregation coefficient, x ray diffraction, and x ray rocking curve are detected, and the results reveal that the single crystal is of high quality. The f-f transitions of Eu3＋ in the host lattice are discussed. The 5D0-7F2 emis- sion transition at 621 nm （red light） is dominant over the 5D0-7F1 emission transitions at 591 and 599 nm （orange light）, agreeing well with the random crystal environment of Eu3＋ ions in a CGA crystal. The decay time of Eu：5D0 is measured to be 1.02 ms. All the results show that the Eu：CGA crystal has good optical char- acterization and promises to be an excellent red- fluorescence material.

A tunable yellow emission from three-band emission of singly doped single-phased phosphor BaY_2S_4:Ho^(3+)

The establishment of an approach to design tunable yellow emission through singly doped single-phased phosphors to obtain white LED-based InGaN chip was reported. BaY2–xS4：xHo3＋ phosphors were prepared by the high temperature solid state reaction and characterized by X-ray diffraction and photoluminescence spectra. Under the excitation of 465 nm,the emission spectra of these phosphors exhibited three sharp emission lines peaked at about 492,543 and 661 nm of Ho3＋ corresponding to 5F3,5F4 （5S2） and 5F5→5I8 transitions,respectively,with comparable intensities,resulting in a yellow light emission. The luminescence mechanism for Ho3＋ in BaY2S4 was explained.

Molecular structure of imidazolate bridged binuclear zinc complex and its single crystal ESR spectra doped with bridged Cu—Zn complex

The X-ray crystal structure of [(dtma)ZnImZn(dtma)]ClO_4·2.5H_2O (Hdtma=4-Diethyl- enetriamineacetic acid) was determined.The crystal is of orthorhombic,space group Pbcn with a- 14.104(5),b=14.897(5),c=25.384(9),and Z=8.The least-square refinement of the structure leads to conventional R factor of 0.066.The magnetic properties of [(dtma)CulmZn(dtma)]CIO_4·2.5H_2O were investigated.From the single crystal ESR spectra of Zn—Im—Zn dimer doped with Cu—Im—Zn complex,the anisotropic g and A tensors and electronic spin-density of the Cu—Zn complex are obtained and the bonding nature of Cu is discussed.