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CRYSTAL GROWTH & DESIGN · 2020 · IF 4.089

Low-Temperature Solution Growth and Characterization of Halogen (Cl, I)-Doped CsPbBr3 Crystals

Fangbao Wang,Hongjian Zhang,Qihao Sun,Ahmed Ben Hafsia,Zhangxuan Chen,Binbin Zhang,Yadong Xu,Wanqi Jie

The all-inorganic halide perovskite CsPbBr3 exhibited extraordinary photoelectric properties as well as great potential for various optic-electronic devices. The introduction of a Cl/I dopant is an effective method to optimize their properties. However, it is still a challenge to grow doped CsPbBr3 single crystals from solution. In this work, we report on the crystal growth of Cl/I-doped CsPbBr3 crystals using the modified inverse temperature crystallization (ITC) method. The components of raw materials and solvent in precursors were precisely tailored. The resulting doping ratio between the actual content and the nominal content are 0.99 and 0.046 for Cl and I, respectively. It indicates that I ion doped crystals exhibit more severe stoichiometric deviation due to the lower decomposition energy. The crystal structure, morphology, and optical properties of doped crystals were also investigated systematically. The {101} and {010} facets of as-grown crystals were influenced by the doping process. PL and UV transmittance spectra exhibited changes in the band gap in Cl/I-doped crystals. Finally, the phase diagram of basic photoelectric properties was determined for CsPb(Br1–nCln)3 crystals and it reveals conductive type changes from the P type to N type with an increase in the doping content of the Cl element. The optimum component of CsPb(Br0.93Cl0.07)3 demonstrates the highest resistivity of 4.3 × 109 Ω cm, an on/off ratio of ∼40, and a mobility of 414 cm2 V–1 s–1 as well as the lowest carrier concentration of 3.57 × 107 cm–3. Our work provides a strategy to grow doped halide perovskite crystals and tailor their optical and electrical properties.

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Applied Sciences-Basel · 2020 ·Vol. 10 ·期 8 ·2663 · IF 2.474

Enhanced Crystal Stabilities of ε-CL-20 via Core-Shell Structured Energetic Composites

Honglei Zhang,Qingjie Jiao,Wanjun Zhao,Xueyong Guo,Dayong Li,Xiaole Sun

Featured ApplicationWe aimed to obtain a dense ε-CL-20/polydopamine core-shell structure by chemical bionic technology that can effectively inhibit the solid–solid phase transition existing for CL-20 crystals and greatly enhance the thermal safety. Obtained well-coated CL-20 particles could be employed in high-energy insensitive polymer bonded explosives (PBX), thus promoting the development of weapons and equipment.Abstract2,4,6,8,10,12-hexanitro-2,4,6,8,10,12-hexaazaisowurtzitane (CL-20) is a widely used high-energy explosive for the application of energetic materials. However, the phase transformation from ε-CL-20 to γ-CL-20 restrains its further application in polymer bonded explosives (PBXs) and propellants. To inhibit the phase transition of CL-20, dopamine was first used in an efficient and facile method of in situ polymerization to passivate CL-20 crystals. The core-shell microcapsule particles were obtained, and the morphological characterization demonstrates the formation of a dense core-shell structure. The differential scanning calorimetry (DSC) and in situ X-ray diffraction (XRD) test results show that the compact and dense coating delays the ε-CL-20 crystal transformation temperature by about 30 °C, which enhances thermal stability. In addition, with the coating via polymers, the friction sensitivity of ε-CL-20 crystals decreases significantly. The findings indicate a successful application of dopamine chemistry in high-energy explosives, which provides an attractive method to modify the properties of CL-20 crystals.Keywords:energetic crystal;phase transition;CL-20;dopamine;core-shell structure

CAS / MDL: 77-86-1
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ACS Applied Nano Materials · 2020 · IF 0

Ultrathin BiOX (X = Cl, Br, I) Nanosheets with Exposed {001} Facets for Photocatalysis

Zidong Wang,Zhe Chu,Chunwei Dong,Ze Wang,Shiyu Yao,Hang Gao,Zhaoyu Liu,Yi Liu,Bai Yang,Hao Zhang

As a family of semiconductor photocatalysts, Sillén-type bismuth oxyhalides (BiOX, X = Cl, Br, I) have attracted widespread interest due to their excellent photocatalytic activity and photoconductivity. However, most current strategies on synthesizing ultrathin 2D BiOX nanosheets (NSs) rely on high temperature and pressure and complex procedures, which seriously confine their large-scale applications. Herein, we develop a simple and facile two-phase method for the synthesis of ultrathin 2D BiOX NSs with highly exposed {001} facets. On the basis of systematically studying the effects of various reaction parameters on the size, thickness, morphology, and composition of the products, the growth mechanism of ultrathin 2D BiOX NSs is presented, which indicates that the suppression of Bi3+ hydrolysis is required for the growth of 2D BiOX NSs with highly exposed {001} facets. The acidic condition prefers the growth of BiOX NSs with ultrathin structure and high crystallinity along the [001] zone axis. By using BiOBr NSs as the example, the photocatalytic activities of ultrathin 2D BiOX NSs are evaluated upon photodegradation of organic compounds and photocatalytic water oxidation. The results show that the organic compound photodegradation is mainly determined by the specific surface area of BiOBr NSs, while the O2 evolution rate of BiOBr NSs for water oxidation is dependent on their photogenerated charge separation efficiency. Because of the larger specific surface area and higher photogenerated charge separation efficiency, BiOBr-acid-0.5 ultrathin 2D NSs exhibits the fastest organic compound photodegradation rate and O2 evolution rate of 445.6 μmol g–1 h–1.

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APPLIED PHYSICS A-MATERIALS SCIENCE & PROCESSING · 2021 ·Vol. 127 ·期 7 ·1-8 · IF 2.584

Research on FTO/CBD-CdS: Cl thin film photodetector with a vertical structure

Zhang Junlin,Wang Yunfan,Zhou Biao,Cao Hongyuan,Yang Xiutao,Li Bing,Zhang Jingquan,Feng Lianghuan,Zeng Guanggen,Zhong Zhengxiang,Ghali Mohsen,Karazhanov Smagul

In this work, CdS thin films were deposited on glass/fluorine-doping tin oxide (FTO) substrates by low-cost chemical bath deposition (CBD), followed by annealing with CdCl 2 -doping (Cl-doping) to fabricate resistive-type photodetectors (PDs) with a vertical structure of glass/FTO/CBD-CdS:Cl/electrode. The effect of annealing with Cl-doping (AwCl) on the various properties of films and the photodetection performance of PDs were systematically characterized by special testing methods. The results revealed that the surface morphology and crystal structure of CBD-CdS:Cl films were improved, accompanied by an enhancement of hexagonal phase (002) crystal plane (wurtzite structure), and the optical bandgap of films can be adjusted between 2.43 and 2.26 eV while the electron activation energy of the films was reduced from 75.9 to 10.3 meV after AwCl. Furthermore, the light responsivity of CBD-CdS:Cl PDs were 0.57, 0.59 and 1.67 A/W under 365, 400 and 530 nm illumination at a bias of −2.0 V, respectively, and the detectivity of photons at corresponding wavelengths were 3.7 × 10 8 , 3.9 × 10 8 and 1.08 × 10 9 Jones. Meanwhile, the PDs showed optimized repeatability and improved sensitivity under periodic illumination. The above results demonstrated that the CBD-CdS:Cl PDs with a vertical structure developed in this work had good detection performance at certain characteristic wavelengths.

CAS / MDL: 10108-64-2
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DALTON TRANSACTIONS · 2018 ·Vol. 47 ·期 29 ·9845-9849 · IF 4.099

Ultrathin CsPbX3 (X = Cl, Br, I) nanoplatelets: solvothermal synthesis and optical spectroscopic properties

Daqin Chen,Xiao Chen,Junni Li,Xinyue Li,Jiasong Zhong

The preparation of CsPbX3 nanoplatelets and the investigation of their optical properties have been rarely reported. Herein, the successful development of all-inorganic CsPbX3 (X = Cl, Br, or I) perovskite quantum dots has been achieved and their unique optical and electrical properties are discussed. Apre-dissolution assisted solvothermal reaction was developed to synthesize ultrathin (∼3 nm) CsPbBr3 nanoplatelets with strong exciton absorption, with a 0.41 eV blue-shifted emission relative to that of CsPbBr3 nanocrystals and a high quantum yield of 28%. Anion exchange allowed the variation of the halogen content of the nanoplatelets and allowed them to retain their shape and size and achieve multi-color emission.

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CERAMICS INTERNATIONAL · 2018 · IF 3.057

Realizing tremendous electrical transport properties of polycrystalline SnSe2 by Cl-doped and anisotropy

Shaohai Wu,Chengyan Liu,Zhengsen Wu,Lei Miao,Jie Gao,Xiaokai Hu,Junliang Chen,Yanyan Zheng,Xiuxia Wang,Chengjin Shen,Hengquan Yang,Xiaoyuan Zhou

SnSe 2 is regarded as an attractive thermoelectric material for its structural and chemical analogy to SnSe that is claimed with the highest ZT in single crystal. In this study, the pure and Cl-doped SnSe 2 polycrystals (3%, 6%, 9% and 12% molar Cl content) were fabricated in four steps that are hydrothermal synthesis , heating purification, diffusion doping, and spark plasma sintering . The phase structure, lamellar morphology and crystallite orientation were studied for the synthesized SnSe 2 powder and the sintered pellets. The structural evolution was traced from the SnSe 2 hexagonal plates of powders to the (001) oriented grains in pellets. The Cl doping into SnSe 2 was verified by phase composition, lattice parameter , element distribution, and chemical valance. The doped Cl increased both the carrier concentration and the mobility. The anisotropic thermoelectric properties of SnSe 2 bulk materials were investigated as functions of temperature from 50 °C to 300 °C and the doping amount, respectively. The Seebeck coefficient was less anisotropic than the electrical and thermal conduction . The grain orientation influenced the anisotropy of the electrical and thermal conductivity at a similar ratio. The power factors were less dependent on temperature with an optimum in-plane 1.06 mW m −1 K −2 and out-of-plane 0.41 mW m −1 K −2 . The highest ZT s of 0.3 were attained at 300 °C in both directions.

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CRYSTENGCOMM · 2017 ·Vol. 19 ·期 30 ·4345-4354 · IF 3.474

sp2CH⋯Cl hydrogen bond in the conformational polymorphism of 4-chloro-phenylanthranilic acid

Meng Liu,Chuming Yin,Peng Chen,Mingtao Zhang,Sean Parkin,Panpan Zhou,Tonglei Li,Faquan Yu,Sihui Long

Chlorine can participate in numerous interactions such as halogen bonding, hydrogen bonding, and London dispersion in the solid state. In this work, we report the influence of a chlorine substituent on the polymorphism of a potential anticancer drug, 4-chloro-phenylanthranilic acid (CPAA). Three polymorphs have been discovered for this compound, and the three forms were characterized by single-crystal X-ray diffraction, power X-ray diffraction (PXRD), FT-IR, and Raman spectroscopy. Both conformational flexibility of the molecule and the sp2CH⋯Cl hydrogen bond seem to lead to the polymorphism of the system. The phase behavior was investigated by differential scanning calorimetry (DSC), with the conclusion that form II converts to III upon heating. A conformational scan shows the conformational minima corresponds to the conformers existing in the polymorphs. Lattice energy calculations show energies of −106.70, −104.72, and −194.42 kJ mol−1 for forms I to III, providing information on relative stability for each form. Hirshfeld analysis revealed that intermolecular interactions such as H⋯H, C⋯H, H⋯Cl, and H⋯O contribute to the stability of the crystal forms.

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Nature Communications · 2022 ·Vol. 13 ·期 1 ·1-9 · IF 17.694

Realizing high-ranged thermoelectric performance in PbSnS2 crystals

Zhan Shaoping,Hong Tao,Qin Bingchao,Zhu Yingcai,Feng Xiang,Su Lizhong,Shi Haonan,Liang Hao,Zhang Qianfan,Gao Xiang,Ge Zhen-Hua,Zheng Lei,Wang Dongyang,Zhao Li-Dong

Great progress has been achieved in p-type SnS thermoelectric compound recently, while the stagnation of the n-type counterpart hinders the construction of thermoelectric devices. Herein, n-type sulfide PbSnS 2 with isostructural to SnS is obtained through Pb alloying and achieves a maximum ZT of ~1.2 and an average ZT of ~0.75 within 300–773 K, which originates from enhanced power factor and intrinsically ultralow thermal conductivity. Combining the optimized carrier concentration by Cl doping and enlarged Seebeck coefficient through activating multiple conduction bands evolutions with temperature, favorable power factors are maintained. Besides, the electron doping stabilizes the phase of PbSnS 2 and the complex-crystal-structure induced strong anharmonicity results in ultralow lattice thermal conductivity. Moreover, a maximum power generation efficiency of ~2.7% can be acquired in a single-leg device. Our study develops a n-type sulfide PbSnS 2 with high performance, which is a potential candidate to match the excellent p-type SnS.

研究领域: 材料科学 · 热电学 · 固体物理
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Nature Communications · 2023 ·Vol. 14 ·期 1 ·1-8 · IF 16.6

Long-term durability of metastable β-Fe2O3 photoanodes in highly corrosive seawater

Liu Changhao,Zhang Ningsi,Li Yang,Fan Rongli,Wang Wenjing,Feng Jianyong,Liu Chen,Wang Jiaou,Hao Weichang,Li Zhaosheng,Zou Zhigang

Durability is one prerequisite for material application. Photoelectrochemical decomposition of seawater is a promising approach to produce clean hydrogen by using solar energy, but it always faces the problem of serious Cl − corrosion. We find that the main deactivation mechanism of the photoanode is oxide surface reconstruction accompanied by the coordination of Cl − during seawater splitting, and the stability of the photoanode can be effectively improved by enhancing the metal-oxygen interaction. Taking the metastable β -Fe 2 O 3 photoanode as an example, Sn added to the lattice can enhance the M–O bonding energy and hinder the transfer of protons to lattice oxygen, thereby inhibiting excessive surface hydration and Cl − coordination. Therefore, the bare Sn/ β -Fe 2 O 3 photoanode delivers a record durability for photoelectrochemical seawater splitting over 3000 h.

研究领域: 材料科学 · 光电化学 · 可再生能源
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Journal of Environmental Chemical Engineering · 2024 · IF 7.4

Oxygen vacancy mediation of BiOX (X=Cl, Br) towards enhanced photocatalytic CO2 reduction activity

Qiong Liu,Chengbo Bai,Die He,Xueting Wu,Yiping Wu,Rong Chen

Surface defects in semiconductors play a significant role in modulating the performance of photocatalytic reactions. However, there is still insufficient exploration regarding the influence of defects on the photocatalytic CO 2 reduction performance. In this study, we achieved controllable construction of oxygen vacancies (OVs) in BiOX (X=Cl, Br) samples through one-step solvothermal treatment in polyols by adjusting the reaction time. The introduction of OVs significantly enhanced the photocatalytic activity of BiOX (X=Cl, Br) for converting CO 2 to CO. Among all the tested BiOX (X=Cl, Br) samples with OVs, BiOCl-OV-2 and BiOBr-OV-2 samples with a moderate amount of OVs exhibited the highest CO yield of 28.51 and 15.22 μmol g cat −1 after 4 hours of irradiation, respectively. Photo-/electrochemical measurements results revealed that engineering OVs into BiOX (X=Cl, Br) effectively adjusted their electronic structure, charge density and separation; however, excessive OVs may slightly degrade their photoelectrochemical properties and thus lead to reduced photocatalytic activity. Furthermore, an appropriate amount of OV was found to enhance both CO 2 adsorption capacity and photo-generated electron reduction ability, thereby further promoting the overall efficiency of photocatalytic CO 2 conversion. Through in situ FTIR spectra analysis, we uncovered the process of photocatalytic conversion from CO 2 to CO.

CAS / MDL: 10035-06-0
研究领域: 材料科学 · 环境科学
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Materials Today · 2025 · IF 22

Continuous production of Cl-terminated MXenes by bubbling chemical vapor growth in molten salt

Jikai Zhang,Yi Tao,Yuxuan Ye,Haiyang Wang,Xinping Wu,Zicheng Luo,Yu Shi,Qi Zhao,Zongju Cheng,Yu Guo,Bin Li,Bo Mai,Qinyou An,Xiansheng Zhang,Zhiguo Du,Shubin Yang

Although 2D transition-metal carbides (MXenes) are usually synthesized by selective etching and chemical vapor deposition approaches, they are limited by the slow reaction kinetics, resulting in their continuous production challenging. Here, we demonstrate a bubbling chemical vapor growth (BCVG) method to continuously produce Cl-terminated MXenes by the reaction of CH 4 and TiCl 4 chemical bubbles with titanium powder in a molten salt. In the molten reaction system, titanium powder would effectively react with TiCl 4 to form highly active [TiCl 6 ] y – with low Ti Cl bond dissociation energies. The multivalent [TiCl 6 ] y – could efficiently incorporate the carbon species from CH 4 to form [Ti 6 CCl 18 ] clusters on the surface of bubbles in a low energy barrier, efficiently promoting the reaction kinetics. Subsequently, Cl-terminated MXenes were produced based on the following condensation reaction of [Ti 6 CCl 18 ] clusters. The resultant MXene (Ti 2 CCl x ) exhibits an expanded structure with strong interfacial polarization between its basal planes and the polymer matrix, delivering a good electromagnetic wave absorption performance with a minimum reflection loss (RL min ) value of –52.2 dB at a thin thickness of 2.84 mm.

CAS / MDL: 7789-24-4
研究领域: 材料科学 · 化学工程
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ACS Catalysis · 2024 · IF 11.3

The Corrosive Cl–-Induced Rapid Surface Reconstruction of Amorphous NiFeCoP Enables Efficient Seawater Splitting

Yang Yu,Wei Zhou,Xiaohan Zhou,Junshu Yuan,Xuewei Zhang,Lijie Wang,Jingyu Li,Xiaoxiao Meng,Fei Sun,Jihui Gao,Guangbo Zhao

Limited by the violent oxidation and corrosion environment of the oxygen evolution reaction (OER) in seawater electrolysis, the design of catalysts with high activity and stability is crucial for improving the hydrogen production performance of the electrolysis cell. Herein, we report taking advantage of corrosive Cl– in seawater to achieve rapid surface reconstruction of amorphous NiFeCoP for stable seawater splitting. The successful introduction of pulse current and P constructs Cl– adsorption active sites to optimize the d-band center and induce the formation of NiFeCo(OH). Density functional theory calculations also verified that NiFeCo(OH) has satisfactory OER activity and chlorine exclusion properties. Benefiting from the electronic structure and reaction intermediate adsorption, NiFeCo(OH) only requires 255.3 mV overpotential to reach a current density of 100 mA cm–2. Meanwhile, the assigned alkaline water electrolysis cell (NFCP || Pt/C) stably operates for 320 h in natural seawater at an industrial current density of 500 mA·cm–2 with a low voltage of 1.806 V. The seawater AEM electrolyzer (NFCP || Pt/C) achieves an improved performance of high activity (2.095 V@500 mA·cm–2) and stable operation (100 h@500 mA·cm–2) to achieve economic seawater splitting. In summary, this work proposes a fast self-reconstruction of a high-performance seawater electrocatalyst for marine hydrogen energy.

研究领域: 材料科学 · 电化学 · 可再生能源
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