Er掺杂PbF_(2)晶体的局域团簇结构与光谱性能研究

本文采用Bridgman法成功生长了一系列Er∶PbF_(2)晶体。利用基于密度泛函理论的第一性原理计算详细研究了Er^(3+)在PbF_(2)晶体中的团簇效应。首次获得了Er∶PbF_(2)晶体的上转换发光特性(发光强度、颜色变化)与团簇结构之间的关系。研究发现,随着Er^(3+)浓度增加,团簇从单聚体向高阶构型演化,Er^(3+)离子之间的距离先减小后增大,这使得上转换发光中的红色发射强度先增大后减小,红绿发光比也在Er^(3+)浓度高于6.5%(摩尔分数)后逐渐减小,即发光颜色可以从红色调整为黄绿色。该研究证明了稀土离子团簇的结构演化可以调控Er∶PbF_(2)的光谱特性,为多色发光材料的设计提供一种新方法。

Efficient CO_(2)Reduction to Formate on CsPbI_(3) Nanocrystals Wrapped with Reduced Graphene Oxide

Transformation of greenhouse gas(CO_(2))into valuable chemicals and fuels is a promising route to address the global issues of climate change and the energy crisis.Metal halide perovskite catalysts have shown their potential in promoting CO_(2)reduction reaction(CO_(2)RR),however,their low phase stability has limited their application perspective.Herein,we present a reduced graphene oxide(rGO)wrapped CsPbI_3 perovskite nanocrystal(NC)CO_(2)RR catalyst(CsPbI_3/rGO),demonstrating enhanced stability in the aqueous electrolyte.The CsPbI_3/rGO catalyst exhibited>92%Faradaic efficiency toward formate production at a CO_(2)RR current density of~12.7 mA cm^(-2).Comprehensive characterizations revealed the superior performance of the CsPbI_3/rGO catalyst originated from the synergistic effects between the CsPbI_3 NCs and rGO,i.e.,rGO stabilized theα-CsPbI_3 phase and tuned the charge distribution,thus lowered the energy barrier for the protonation process and the formation of~*HCOO intermediate,which resulted in high CO_(2)RR selectivity toward formate.This work shows a promising strategy to rationally design robust metal halide perovskites for achieving efficient CO_(2)RR toward valuable fuels.

Development strategies and improved photocatalytic CO_(2) reduction performance of metal halide perovskite nanocrystals

In recent years,photocatalytic CO_(2)reduction reaction(CRR) has attracted much scientific attention to overcome energy and environmental issues by converting CO_(2)into high-value-added chemicals utilizing solar energy.Metal halide perovskite(MHP) nanocrystals(NCs) are recognized as an ideal choice for CRR owing to their outstanding optoelectronic properties.Although great efforts have been devoted to designing more effective photocatalysts to optimize CRR performance,severe charge recombination,instability,and unsatisfactory activity have become major bottlenecks in developing perovskite-based photocatalysts.In this review,we mainly focus on the recent research progress in the areas of relevance.First,a brief insight into reaction mechanisms for CRR and structural features of MHPs are introduced.Second,efficient modification approaches for the improvement of the photocatalytic activity and stability of the perovskite-based catalysts are comprehensively reviewed.Third,the state-of-the-art achievements of perovskite-based photocatalysts for CRR are systematically summarized and discussed,which are focused on the modification approaches,structure design,and the mechanism of the CO_(2)reduction process.Lastly,the current challenges and future research perspectives in the design and application of perovskite materials are highlighted from our point of view to provide helpful insights for seeking breakthroughs in the field of CRR.This review may provide a guide for scientists interested in applying perovskite-based catalysts for solar-to-chemical energy conversion.

Enabling High-Performance Sodium Battery Anodes by Complete Reduction of Graphene Oxide and Cooperative In-Situ Crystallization of Ultrafine SnO_(2)Nanocrystals

The main bottleneck against industrial utilization of sodium ion batteries(SIBs)is the lack of high-capacity electrodes to rival those of the benchmark lithium ion batteries(LIBs).Here in this work,we have developed an economical method for in situ fabrication of nanocomposites made of crystalline few-layer graphene sheets loaded with ultrafine SnO_(2)nanocrystals,using short exposure of microwave to xerogel of graphene oxide(GO)and tin tetrachloride containing minute catalyzing dispersoids of chemically reduced GO(RGO).The resultant nanocomposites(SnO_(2)@MWG)enabled significantly quickened redox processes as SIB anode,which led to remarkable full anode-specific capacity reaching 538 mAh g^(−1)at 0.05 A g^(−1)(about 1.45 times of the theoretical capacity of graphite for the LIB),in addition to outstanding rate performance over prolonged charge–discharge cycling.Anodes based on the optimized SnO_(2)@MWG delivered stable performance over 2000 cycles even at a high current density of 5 A g^(−1),and capacity retention of over 70.4%was maintained at a high areal loading of 3.4 mg cm^(−2),highly desirable for high energy density SIBs to rival the current benchmark LIBs.

Ultrasmall NiS_(2)Nanocrystals Embedded in Ordered Macroporous Graphenic Carbon Matrix for Efficiently Pseudocapacitive Sodium Storage

Sodium-ion hybrid capacitor(SIHC)is one of the most promising alternatives for large-scale energy storage due to its high energy and power densities,natural abundance,and low cost.However,overcoming the imbalance between slow Na^(+)reaction kinetics of battery-type anodes and rapid ion adsorption/desorption of capacitive cathodes is a significant challenge.Here,we propose the high-rate-performance NiS_(2)@OMGC anode material composed of monodispersed NiS_(2) nanocrystals(8.8±1.7 nm in size)and N,S-co-doped graphenic carbon(GC).The NiS_(2)@OMGC material has a three-dimensionally ordered macroporous(3DOM)morphology,and numerous NiS_(2) nanocrystals are uniformly embedded in GC,forming a core-shell structure in the local area.Ultrafine NiS_(2) nanocrystals and their nano-microstructure demonstrate high pseudocapacitive Na-storage capability and thus excellent rate performance(355.7 mAh/g at 20.0 A/g).A SIHC device fabricated using NiS_(2)@OMGC and commercial activated carbon(AC)cathode exhibits ultrahigh energy densities(197.4 Wh/kg at 398.8 W/kg)and power densities(43.9 kW/kg at 41.3 Wh/kg),together with a long life span.This outcome exemplifies the rational architecture and composition design of this type of anode material.This strategy can be extended to the design and synthesis of a wide range of high-performance electrode materials for energy storage applications.

Boosting the catalytic activity toward oxygen reduction via a heterostructure of porous iron oxide-decorated 2D NiO/NG nanosheets

As a noble metal substitute,two-dimensional(2D)hierarchical nano-frame structures have attracted great interest as candidate catalysts due to their remarkable advantages-high intrinsic activity,high electron mobility,and straightforward surface functionalization.Therefore,they may replace Pt-based catalysts in oxygen reduction reaction(ORR)applications.Herein,a simple method is developed to design hierarchical nano-frame structures assembled via 2D NiO and N-doped graphene(NG)nanosheets.This procedure can yield nanostructures that satisfy the criteria correlated with improved electrocatalytic performance,such as large surface area,numerous undercoordinated atoms,and high defect densities.Further,porous NG nanosheet architectures,featuring NiO nanosheets densely coordinated with accessible holey Fe_(2)O_(3) moieties,can enhance mesoporosity and balance hydrophilicity.Such improvements can facilitate charge transport and expose formerly inaccessible reaction sites,maximizing active site density utilization.Density functional theory(DFT)calculations reveal favored O_(2) adsorption and dissociation on Fe_(2)O_(3) hybrid structures when supported by 2D NiO and NG nanomaterials,given 2D materials donated charge to Fe_(2)O_(3) active sites.Our systematic studies reveal that synergistic contributions are responsible for enriching the catalytic activity of Fe_(2)O_(3)@NiO/NG in alkaline media-encompassing internal voids and pores,unique hierarchical support structures,and concentrated N-dopant and bimetallic atomic interactions.Ultimately,this work expands the toolbox for designing and synthesizing highly efficient 2D/2D shelled functional nanomaterials with transition metals,endeavoring to benefit energy conversion and related ORR applications.

蓝光激发的KMgF_(3)∶Cr^(3+)/Ni^(2+)基透明微晶玻璃超宽带近红外发光

近红外光谱技术在食品科学、信息安全、生物医疗等重大国计民生领域的应用对近红外光源提出了越来越高的要求。研发具有高效超宽带发射的近红外光源因此成为一项重要且迫切的研究课题。本文采用熔融淬火法在氟硅酸盐玻璃体系SiO_(2)-K_(2)CO_(3)-KF·2H_(2)O-MgF_(2)中成功析出了钙钛矿型KMgF_(3)纳米晶体。通过改变玻璃组分和热处理温度可以调控氟化物纳米晶相的析出,得到析晶和透明度最佳的微晶玻璃样品。玻璃中KMgF_(3)纳米晶体为Cr^(3+)和Ni^(2+)提供了稳定的八面体配位和低声子能量发光环境,在450 nm蓝光激发下,基于Cr^(3+)到Ni^(2+)的能量传递实现了Cr^(3+)(700~1200 nm)和Ni^(2+)(1400~1700 nm)双宽带近红外发射,并且双宽带近红外发光强度随离子掺杂浓度而可调变化。荧光光谱和荧光衰减曲线表征证明了Cr^(3+)到Ni^(2+)的能量传递过程,对应的能量传递效率为52.2%,能量传递机制为电子偶极-四极相互作用。研究结果不仅可以为系统掌握透明光学材料的超宽带发光规律提供基础数据,同时有助于设计开发低成本、高效率的近红外宽带光源。

PbF_(2)·SiO_(2)基玻璃陶瓷的溶胶-凝胶法制备及结构转变研究

采用溶胶-凝胶法制备了 PbF2?SiO2纳米晶玻璃陶瓷块体;利用 TG-DSC 和 IR 技术分析了干凝胶在热处理过程中有机基团的分解及内部原子键合方式的演变;结合 XRD 和 TEM 研究了凝胶玻璃中 PbF2纳米晶粒的长大过程,并分析了 Er3+掺杂的影响。结果表明,采用此方法制备的 PbF2?SiO2纳米晶玻璃陶瓷具有较好的成形性,晶化温度在 320℃左右;经 480℃热处理,镶嵌在玻璃基体中的 PbF2晶粒尺度约为 10～25nm,材料透明性良好。在 PbF2?SiO2系统中掺入少量的 Er3+,将提高 PbF2的晶化温度,降低玻璃陶瓷的显微硬度;掺杂可能对 PbF2晶粒表面原子的活性起抑制作用,阻碍晶粒的表面迁移,使晶粒的生长速度明显降低。

新型中红外激光晶体Er^(3+)/Ho^(3+)/Eu^(3+)∶PbF_(2)的生长和性能

采用垂直布里奇曼法成功生长了Er^(3+)/Ho^(3+)/Eu^(3+)三掺杂PbF_(2)的中红外激光晶体。该晶体在980 nm泵浦下,首次获得了从2600~3200 nm的宽带中红外发光,其半高宽(FWHM)为300 nm,这是Er^(3+)的2.7μm发射峰(2600~2950 nm)和Ho^(3+)的2.9μm发射峰(2800~3200 nm)叠加的结果。此外,失活离子Eu^(3+)的引入可以有效克服Er^(3+)和Ho^(3+)离子的自终止瓶颈效应。研究发现,与Er^(3+)/Ho^(3+)∶PbF_(2)晶体相比,Er^(3+)/Ho^(3+)/Eu^(3+)∶PbF_(2)晶体具有更高的荧光分支比,在Er^(3+):^(4)I_(11/2)→^(4)I_(13/2)跃迁为18.7%和Ho^(3+):^(5)I_(6)→^(5)I_(7)跃迁为18.0%;以及有更大的发射截面,在2745 nm时为0.621×10^(-20) cm^(2),在2905 nm时为0.728×10^(-20) cm^(2)。这些有利的光谱特性表明,Er^(3+)/Ho^(3+)/Eu^(3+)∶PbF_(2)晶体在商用980 nm激光二极管泵浦下,可能是2.6~3.2μm中红外激光器的一种有前景的材料。

Polymer waveguide thermo-optical switch with loss compensation based on NaYF_4: 18% Yb^(3+), 2% Er^(3+) nanocrystals

A polymer waveguide thermo-optical switch with loss compensation based on NaYF_4： 18% Yb^（3＋）, 2% Er^（3＋）nanocrystals, fabricated by traditional semiconductor processes, has been investigated. NaYF4： 18% Yb^（3＋）, 2% Er^（3＋）nanocrystals were prepared by a pyrolysis method. The morphology and luminescent properties of the nanocrystals were characterized.The nanocrystals were doped into SU-8 as the core material of an optical waveguide amplifier. The size of the device was optimized for its optical and thermal fields as well as its transmission characteristics. The device was fabricated on a silica substrate by spin coating, photolithography, and wet etching. The insertion loss of the switch device is～15 dB. The rise and fall times of the device are 240 μs and 380 μs, respectively, as measured by application of a 304 Hz square wave voltage. The extinction ratio of the device is about 14 dB at an electrode-driving power of 7 mW. When the pump light power is 230 mW and the signal light power is 0.1 mW, the loss compensation of the device is 3.8 dB at a wavelength of1530 nm. Optical devices with loss compensation have important research significance.

(N,F)-codoped TiO_2 Nanocrystals as Visible Light-activated Photocatalyst

（N, F）-codoped anatase TiO2 nanocrystals with active visible light response were prepared by using a simple sol-gel approach. X-ray photoelectron spectroscopy measurements suggested that the substitutional N and F species replaced the lattice oxygen atoms in TiO2 nanocrystals. Such nanocrystals showed strong absorption from 400 to 550 nm, which was mainly induced by nitrogen doping. The phase transformation from anatase to rutile was hindered by fluorine doping at high calcination temperatures, which was verified by XRD patterns. The N2 adsorption-desorption isotherms revealed the absence of mesopores in these nanocrystals. The （N, F）- codoped TiO2 nanocrystals showed satisfying photocatalytic activity on the photo-degradation of methylene blue under visible light.

Well-dispersed SnO2 nanocrystals on N-doped carbon nanowires as efficient electrocatalysts for carbon dioxide reduction

The conversion of carbon dioxide into valuable organic compounds is a highly promising approach to address the energy issues and environmental problems(e.g., global warming). Herein, we presents a facile and efficient method to prepare highly dense and well-dispersed SnO2 nanocrystals on 1 D N-doped carbon nanowires as advanced catalysts for the efficient electroreduction of CO2 to formate. The ultrasmall SnO2 coated on the N-doped carbon nanowires(SnO2@N-CNW) has been synthesized via the simple hydrothermal treatment coupled with a pyrolysis process. The unique structure enables to expose the active tin oxide and also provides the facile pathways for rapid transfer of electron and electrolyte along with the highly porous carbon foam composed with interconnected carbon nanowires. Therefore, SnO2@NCNW electrocatalyst exhibits good durability and high selectivity for formate formation with a Faradaic efficiency of ca. 90%. This work demonstrates a simple method to rationally design high-dense tin oxide nanocrystals on the conductive carbon support as advanced catalysts for CO2 electroreduction.

Synthesis and Photoluminescence of Ln^(3+) Doped TiO_2 Nanocrystal

Eu3+ doped TiO2 nanocrystals were prepared by the hydrothermal method and characterized by XRD, ESEM, IR, UV absorption and emission spectra. XRD and ESEM micrograph revealed that the samples are in pure rutile phase. Emission spectra under 355 nm radiative were measured to characterize the spectroscopic properties, which showed that the samples probably contain trace Tb3+ ions. The energy transfer mechanism from rutile TiO2 to the 4f shell of Tb3+ and Eu3+ was discussed in connection with the excitation and emission properties of the samples.

Confining MoS_(2) nanocrystals in MOF-derived carbon for high performance lithium and potassium storage

Developing an efficient synthesis protocol to simultaneously control 2D nanomaterials’size and dispersion is the pivot to optimize their electrochemical performance.Herein,we report the synthesis of uniform MoS_(2) nanocrystals well-anchored into the void space of porous carbon(donated as MoS_(2)3C hybrids)by a simple confined reaction in metal–organic framework(MOF)during carbonization process.The strong confinement effect refrain MoS2 growth and aggregation,generating abundant active centers and edges,which contribute fast lithium/potassium reaction kinetics.In addition to the hybridization with the derived carbon,the MoS_(2)3C hybrids exhibit rapid Liþtransfer rate(~109 cm^(2) s 1)and greatly improved electronic conductivity.Consequently,the MoS23C hybrids show ultrafast rate performances and satisfactory cycling stabilities as anode materials for both lithium and potassium ion batteries.This work demonstrates a universal tactic to achieve high dispersive 2D nanomaterials with tailorable particle size.

Preparation of nanocrystalline Na_2ZrO_3 for high-temperature CO_2 acceptors:chemistry and mechanism

Nanocrystalline Na2ZrO3 was demonstrated as a promising acceptor for CO2 capture at elevated temperatures. The mechanism of nanocrystalline Na2ZrO3 formation from the soft-chemistry route is elucidated by varying precursors, preparation methods, and calciantion temperatures, combining detailed characterizations by X-ray diffraction （XRD） and scanning electron microscope （SEM） at different steps in the process. The results revealed that the drying method such as spraying drying and simple evaporation-drying did not influence the final product prop- erties. However both Na and Zr precursors had remarkable influences on the Na2ZrO3 formation. The solid reaction of Na intermediate and nanocrystalline ZrO2 in the calcination was identified as the key step for the Na2ZrO3 formation, where the formation of molten phase Na intermediate was found to be crucial to facilitate the solid reaction. We provided principles for rational design of the chemistry for the Na2ZrO3 formation where the formation of Na intermediate with low melting points is essential. Pure nanocrystalline Na2ZrO3 can be synthesized from a mixture containing sodium nitrate and zirconoxy citrate via the formation of NaNO3 with low melting point. However, it is not possible to form pure nanocrystalline Na2ZrO3 at relatively low temperatures from the mixtures of NaAc/ZrO（NO3）2 or NaCA/ZrOC12 due to the formation of Na2CO3 and NaC1 with high melting points.

Importance of ligands on TiO_2 nanocrystals for perovskite solar cells

The fabrication of high-quality electron-selective layers at low temperature is a prerequisite to realizing efficient flexible and tandem perovskite solar cells （PSCs）. A colloidal-quantum-dot ink that contains TiO2 nanocrystals enables the deposition of a flat film with matched energy level for PSCs; however, the selection of ligands on the TiO2 surface is still unexplored. Here, we systematically studied the effect of the titanium diisopropoxide bis（acetylacetonate） （TiAc2） ligand on the performance of PSCs with a planar n-i-p architecture. We prepared TiO2 nanocrystals from TiCI4 and ethyl alcohol with C1- ligands attached on its surface and we found that a tiny amount of TiAc2 treatment of as-prepared TiO2 nanocrystals in a mixed solution of chloroform and methyl alcohol can enhance PSC power conversion efficiency （PCE） from 14.7% to 18.3%. To investigate the effect of TiAc2 ligand on PSCs, TiO2 samples with different TiAc2 content were prepared by adding TiAc2 into the as-obtained TiO2 nanocrystal solution. We use x-ray photoelectron spectroscopy to identify the content of C1 so as to reveal that C1 ligands can be substituted by TiAc2. We speculate that the improvement in PCE originates from amorphous TiO2 formation on the TiO2 nanocrystal surface, whereby a single-molecule layer of amorphous TiO2 facilitates charge transfer between the perovskite film and the TiO2 electronic transport layer, but excessive TiAc2 lowers the PSC performance dramatically. We further prove our hypothesis by x-ray diffraction measurements. We believe the PCE of PSCs can be further improved by carefully choosing the type and changing the content of surface ligands on TiO2 nanocrystal.

Upconversion Emission and Paramagnetism of Colloid Ba2 ErF7 and Ba2 ErF7 :Yb^(3+) Nanocrystals Synthesized with Solvothermal Method

Ultrasmall near-monodisperse Ba2ErF7 nanocrystals with average crystal size 9.6 nm were synthesized with solvothermal method. The X-ray diffraction （XRD） and transmission electron microscopy （TEM） assays reveal that the as-synthesized Ba2ErF7 nanocrystals are of the cubic structure with the cell parameter of 5.943 A, instead of the reported orthorhombic and tetragonal structure. Two emission bands originated from 2Hwj4H3/2 → 4F5/2 and 4F9/2 ----＋ 4115,2 of Er3＋ can be observed under a 980 nm laser excitation. The magnetic mass susceptibility of the as-synthesized BazErF7 nanocrystals reaches 4.293 × 10-5 emu g-1 Oe-1.

2H-SiC Dendritic Nanocrystals In Situ Formation from Amorphous Silicon Carbide under Electron Beam Irradiation

Under electron beam irradiation, the in-situ formation of 2H-SiC dentritic nanocrystals from amorphous silicon carbide at room temperature was observed. The homogenous transition mainly occurs at the thin edge and on the surface of specimen where the energy obtained from electron beam irradiation is high enough to cause the amorphous crystallizing into 2H-SiC.

Grain Growth Kinetics of SnO_2 Nanocrystals Synthesized by Precipitation Method

Monodispersed spheroidal SnO2 nanocrystals with the grain size of 8-30 nm were synthesized by the precipitation method using SnCl4·5H2O （stannic chloride hydrate） as raw materials.Differential scanning calorimetry/thermogravimetry （DSC/TG）,X-ray diffraction （XRD） and transmission electron microscope （TEM） were used to characterize the structure of SnO2 nanocrystals.The influences of the calcination temperature and time on the lattice constant,the lattice distortion and the grain size of SnO2 nanocrystals were discussed based on the XRD results.The grain growth kinetics of SnO2 nanocrystals during calcination process was simulated with a conventional grain growth model which only took into account of diffusion and with a new isothermal model proposed by our group,which took into account of both diffusion and surface reactions.Using conventional model,the grain growth rate constant of SnO2 crystals is 1.55×104nm5/min with a pre-exponential factor of 5 and an activation energy of 108.62 kJ/mol.Compared with the convention model,the new isothermal model is more realistic in reflecting the grain growth behavior of SnO2 nanocrystals during the calcination process.This indicates that the grain growth of SnO2 nanocrystals is controlled by both diffusion and reaction factors,and the effect of surface reactivity on the grain growth of SnO2 nanocrystals could not be ignored.A combined activation energy estimated with the new isothermal model is 53.46 kJ/mol.