Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficien...Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficiency.Herein,we explore an economic and environmentally friendly method for synthesizing hierarchical NaX zeolite that exhibits improved catalytic performance in the Knoevenagel condensation reaction for producing the useful fine chemical 2-cyano-3-phenylacrylate.The synthesis was achieved via a low-temperature activation of kaolinite and subsequent in-situ transformation strategy without any template or seed.Systematic characterizations reveal that the synthesized NaX zeolite has both intercrystalline and intra-crystalline mesopores,smaller crystal size,and larger external specific surface area compared to commercial NaX zeolite.Detailed mechanism investigations show that the inter-crystalline mesopores are generated by stacking smaller crystals formed from in-situ crystallization of the depolymerized kaolinite,and the intra-crystalline mesopores are inherited from the pores in the depolymerized kaolinite.This synthesis strategy provides an energy-saving and effective way to construct hierarchical zeolites,which may gain wide applications in fine chemical manufacturing.展开更多
Low-temperature,ambient processing of high-quality CsPbBr_(3)films is demanded for scalable production of efficient,low-cost carbon-electrode perovskite solar cells(PSCs).Herein,we demonstrate a crystal orientation en...Low-temperature,ambient processing of high-quality CsPbBr_(3)films is demanded for scalable production of efficient,low-cost carbon-electrode perovskite solar cells(PSCs).Herein,we demonstrate a crystal orientation engineering strategy of PbBr_(2)precursor film to accelerate its reaction with CsBr precursor during two-step sequential deposition of CsPbBr_(3)films.Such a novel strategy is proceeded by adding CsBr species into PbBr_(2)precursor,which can tailor the preferred crystal orientation of PbBr_(2)film from[020]into[031],with CsBr additive staying in the film as CsPb_(2)Br_(5)phase.Theoretical calculations show that the reaction energy barrier of(031)planes of PbBr_(2)with CsBr is lower about 2.28 eV than that of(O2O)planes.Therefore,CsPbBr_(3)films with full coverage,high purity,high crystallinity,micro-sized grains can be obtained at a low temperature of 150℃.Carbon-electrode PSCs with these desired CsPbBr_(3)films yield the record-high efficiency of 10.27%coupled with excellent operation stability.Meanwhile,the 1 cm^(2)area one with the superior efficiency of 8.00%as well as the flexible one with the champion efficiency of 8.27%and excellent mechanical bending characteristics are also achieved.展开更多
A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal cry...A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal crystallinity and purity can be obtained by systematically adjusting feed composition and synthesis conditions.Characterizations show that Fe ZSM-22 zeolite synthesized with OSDA-free owns high crystallinity,obvious thin needle-shaped morphology and high Bronsted/Lewis acid ratio.Significantly,when used for n-octane hydroisomerization reaction,its derived catalyst exhibits the best catalytic performance reflected by the highest selectivity to C_(8)isomers compared to the two reference catalysts prepared based on a Fe-containing and a Fe-free ZSM-22 synthesized through an OSDA-directed route from natural diatomite and conventional chemicals,respectively.This work provides an alternative route to sustainably synthesizing heteroatomic zeolites with high performance.展开更多
For lithium-sulfur batteries(Li-S batteries),a high-content electrolyte typically can exacerbate the shuttle effect,while a lean electrolyte may lead to decreased Li-ion conductivity and reduced catalytic conversion e...For lithium-sulfur batteries(Li-S batteries),a high-content electrolyte typically can exacerbate the shuttle effect,while a lean electrolyte may lead to decreased Li-ion conductivity and reduced catalytic conversion efficiency,so achieving an appropriate electrolyte-to-sulfur ratio(E/S ratio)is essential for improving the battery cycling efficiency.A quasi-solid electrolyte(COF-SH@PVDF-HFP)with strong adsorption and high catalytic conversion was constructed for in situ covalent organic framework(COF)growth on highly polarized polyvinylidene fluoride-hexafluoropropylene(PVDF-HFP)fibers.COF-SH@PVDF-HFP enables efficient Li-ion conductivity with low-content liquid electrolyte and effectively suppresses the shuttle effect.The results based on in situ Fourier-transform infrared,in situ Raman,UV–Vis,X-ray photoelectron,and density functional theory calculations confirmed the high catalytic conversion of COF-SH layer containing sulfhydryl and imine groups for the lithium polysulfides.Lithium plating/stripping tests based on Li/COF-SH@PVDF-HFP/Li show excellent lithium compatibility(5 mAh cm^(-2) for 1400 h).The assembled Li-S battery exhibits excellent rate(2 C 688.7 mAh g^(-1))and cycle performance(at 2 C of 568.8 mAh g^(-1) with a capacity retention of 77.3%after 800 cycles).This is the first report to improve the cycling stability of quasi-solid-state Li-S batteries by reducing both the E/S ratio and the designing strategy of sulfhydryl-functionalized COF for quasi-solid electro-lytes.This process opens up the possibility of the high performance of solid-state Li-S batteries.展开更多
NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer.Effects of alkalinity ranging from 0.38 to 0.55(n(Na_(2)O...NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer.Effects of alkalinity ranging from 0.38 to 0.55(n(Na_(2)O)/n(SiO_(2)))on the relative crystallinity,textural properties and crystallization kinetics were investigated.The results show that alkalinity exerts a nonmonotonic influence on the relative crystallinity and textural properties,which exhibit a maximum at the alkalinity of 0.43.The nucleation kinetics are studied by fitting the experimental data of relative crystallinity with the Gualtieri model.It is shown that the nucleation rate constant increases with increasing alkalinity,while the duration period of nucleation decreases with increasing alkalinity.For n(Na_(2)O)/n(SiO_(2))ratios ranging from 0.38 to 0.55,the as-synthesized NaY zeolites exhibit narrower crystal size distributions with the increase in alkalinity.The growth rates determined from the variations of average crystal size with time are 51.09,157.50,46.17 and 24.75 nm·h^(-1),respectively.It is found that the larger average crystal sizes at the alkalinity of 0.38 and 0.43 are attributed to the dominant role of crystal growth over nucleation.Furthermore,the combined action of prominent crystal growth and the longer duration periods of nucleation at the alkalinity of 0.38 and 0.43 results in broader crystal size distributions.The findings demonstrate that control of the properties of NaY zeolite and the crystallization kinetics can be achieved by conducting the crystallization process in an appropriate range of alkalinity of the reaction mixture.展开更多
The practical application of lithium-sulfur(Li-S)batteries,as promising next-generation batteries,is hindered by their shuttle effect and the slow redox kinetics.Herein,a tungsten and molybdenum nitride heterostructur...The practical application of lithium-sulfur(Li-S)batteries,as promising next-generation batteries,is hindered by their shuttle effect and the slow redox kinetics.Herein,a tungsten and molybdenum nitride heterostructure functionalized with hollow metal-organic framework-derived carbon(W_(2)N/Mo_(2)N)was proposed as the sulfur host.The hollow spherical structure provides storage space for sulfur,enhances electrical conductivity,and inhibits volume expansion.The metal atoms in the nitrides bonded with lithium polysulfides(Li PSs)through Lewis covalent bonds,enhancing the high catalytic activity of the nitrides and effectively reducing the energy barrier of Li PSs redox conversion.Moreover,the high intrinsic conductivity of nitrides and the ability of the heterostructure interface to accelerate electron/ion transport improved the Li+transmission.By leveraging the combined properties of strong adsorption and high catalytic activity,the sulfur host effectively inhibited the shuttle effect and accelerated the redox kinetics of Li PSs.High-efficiency Li+transmission,strong adsorption,and the efficient catalytic conversion activities of Li PSs in the heterostructure were experimentally and theoretically verified.The results indicate that the W_(2)N/Mo_(2)N cathode provides stable,and long-term cycling(over 2000 cycles)at 3 C with a low attenuation rate of 0.0196%per cycle.The design strategy of a twinborn nitride heterostructure thus provides a functionalized solution for advanced Li-S batteries.展开更多
目的 探瘤Sp ECT/CT标准化摄取值(sta n d ard upta ke value,SUV)联合超声在预测甲状腺结节良恶性中的价值。方法选取2022年4月至2024年5月经超声诊断为非囊性、甲状腺显像诊断为“非热结节”的92例甲状腺结节患者,择期行甲状腺甲氧基...目的 探瘤Sp ECT/CT标准化摄取值(sta n d ard upta ke value,SUV)联合超声在预测甲状腺结节良恶性中的价值。方法选取2022年4月至2024年5月经超声诊断为非囊性、甲状腺显像诊断为“非热结节”的92例甲状腺结节患者,择期行甲状腺甲氧基异丁基异腈(^(99m)Tc-Ml BI)亲肿瘤显像及定量S P E CT/CT检查,采用定参数自动勾画方式分别勾画感兴趣区(ROI)获得SUV值,以病理结果为“金标准”。采用ROC曲线对SUV在对甲状腺结节良恶性进行评估时的灵敏度和特异度进行分析,获得诊断界值。采用配对χ^(2)检验比较分析定量SPECT/CT SUV值、超声及联合诊断对甲状腺结节良恶性的鉴别诊断效能。结果92例患者中甲状腺恶性结节32例,良性结节60例,甲状腺恶性组平均标准化摄取值(SUV mean)和最大标准化摄取值(SUVmax)高于良性组,差异有统计学意义;ROC曲线结果提示SUVmean、SUVmax的诊断界值、曲线下面积(AUC)分别为2.57g/mL、 0.840和5.17g/mL、0.892,SUVmax的诊断效能更高。SUVmax组、超声组及联合组诊断灵敏度分别为53.12%、75.00%、87.5%,特异度分别力88.33%、78.33%、83.33%,准确度分别为76.09%、77.17%、84.78%。配对χ^(2)检验结果表明,超声和SUVmax组诊断的准确性有显著性差异(χ^(2)=20.488,P<0.01),联合诊断的准确性优于SUVmax和超声(χ^(2)=46.142,P<0.01;χ^(2)=58.536,P<0.01)。ROC曲线结果显示三组的AUC分别为0.707、0.767、0.854,联合诊断效能最高。结论精准定量SPECT/CTSUVmax值尤其是与超声联合诊断可以在穿刺活检或手术确诊前提高甲状腺恶性结节的检出率和诊断效能,其单独鉴别诊断甲状腺结节良恶性的诊断界值为5.17g/m L。展开更多
文摘目的:对下颌第一磨牙拔除后行种植修复的病例进行回顾性研究,探索重度牙周破坏(advanced periodontal defect,APD)对拔牙后种植手术方式的影响。方法:纳入下颌第一磨牙拔除后自然愈合3~12个月行种植手术的患者176例,共179个种植位点,进行回顾性分析,记录患者年龄、性别、缺牙时间以及拔牙时是否有APD。采用多因素Logistic回归,分析拔牙前APD是否是种植时行引导性骨再生(guided bone regeneration,GBR)的风险因素。结果:对年龄、性别、缺牙时间等因素校正后,结果显示,有APD的下颌第一磨牙,种植时行GBR的风险是无APD位点的4.738倍(95%可信区间:1.650~13.609,P<0.05)。结论:APD的下颌第一磨牙拔除后,种植手术时行GBR的可能性更大。
基金The financial supports from the National Natural Science Foundation of China (22178059, 22208054 and 22072019)Natural Science Foundation of Fujian Province, China (2020J01513)+1 种基金Sinochem Quanzhou Energy Technology Co., Ltd. (ZHQZKJ-19-F-ZS0076)Qingyuan Innovation Laboratory (00121002)
文摘Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficiency.Herein,we explore an economic and environmentally friendly method for synthesizing hierarchical NaX zeolite that exhibits improved catalytic performance in the Knoevenagel condensation reaction for producing the useful fine chemical 2-cyano-3-phenylacrylate.The synthesis was achieved via a low-temperature activation of kaolinite and subsequent in-situ transformation strategy without any template or seed.Systematic characterizations reveal that the synthesized NaX zeolite has both intercrystalline and intra-crystalline mesopores,smaller crystal size,and larger external specific surface area compared to commercial NaX zeolite.Detailed mechanism investigations show that the inter-crystalline mesopores are generated by stacking smaller crystals formed from in-situ crystallization of the depolymerized kaolinite,and the intra-crystalline mesopores are inherited from the pores in the depolymerized kaolinite.This synthesis strategy provides an energy-saving and effective way to construct hierarchical zeolites,which may gain wide applications in fine chemical manufacturing.
基金the financial support from the National Key R&D program of China(2021YFF0500501 and 2021YFF0500504)the Fundamental Research Funds for the Central Universities(YJS2213 and JB211408)+1 种基金the National Natural Science Foundation of China(61874083)the Joint Research Funds of Department of Science&Technology of Shaanxi Province and Northwestern Polytechnical University(No.2020GXLH-Z-014)
文摘Low-temperature,ambient processing of high-quality CsPbBr_(3)films is demanded for scalable production of efficient,low-cost carbon-electrode perovskite solar cells(PSCs).Herein,we demonstrate a crystal orientation engineering strategy of PbBr_(2)precursor film to accelerate its reaction with CsBr precursor during two-step sequential deposition of CsPbBr_(3)films.Such a novel strategy is proceeded by adding CsBr species into PbBr_(2)precursor,which can tailor the preferred crystal orientation of PbBr_(2)film from[020]into[031],with CsBr additive staying in the film as CsPb_(2)Br_(5)phase.Theoretical calculations show that the reaction energy barrier of(031)planes of PbBr_(2)with CsBr is lower about 2.28 eV than that of(O2O)planes.Therefore,CsPbBr_(3)films with full coverage,high purity,high crystallinity,micro-sized grains can be obtained at a low temperature of 150℃.Carbon-electrode PSCs with these desired CsPbBr_(3)films yield the record-high efficiency of 10.27%coupled with excellent operation stability.Meanwhile,the 1 cm^(2)area one with the superior efficiency of 8.00%as well as the flexible one with the champion efficiency of 8.27%and excellent mechanical bending characteristics are also achieved.
基金the financial supports from the National Natural Science Foundation of China(22322803,22178059,22208054,22221005,22072019)Key Technologies Innovation and Industrialization Projects of Fujian Province(2022G031)Qingyuan Innovation Laboratory(00121002,00523005)。
文摘A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal crystallinity and purity can be obtained by systematically adjusting feed composition and synthesis conditions.Characterizations show that Fe ZSM-22 zeolite synthesized with OSDA-free owns high crystallinity,obvious thin needle-shaped morphology and high Bronsted/Lewis acid ratio.Significantly,when used for n-octane hydroisomerization reaction,its derived catalyst exhibits the best catalytic performance reflected by the highest selectivity to C_(8)isomers compared to the two reference catalysts prepared based on a Fe-containing and a Fe-free ZSM-22 synthesized through an OSDA-directed route from natural diatomite and conventional chemicals,respectively.This work provides an alternative route to sustainably synthesizing heteroatomic zeolites with high performance.
基金This research was supported by the National Natural Science Foundation of China(52202104)the Joint Funds of the Zhejiang Provincial Natural Science Foundation of China(LZY23B030002)+5 种基金the China Postdoctoral Science Foundation(2021T140433,2020M683408)the Quzhou Science and Technology Bureau Project(2022D015,2023D023)the International Cooperation Projects of Sichuan Provincial Department of Science and Technology(2021YFH0126)the Fundamental Research Funds for the Central Universities(ZYGX2020ZB016)the Key Research and Development Program of Yunnan Province China(202103AA080019)Yunnan Major Scientific and Technological Projects(202202AG050003).
文摘For lithium-sulfur batteries(Li-S batteries),a high-content electrolyte typically can exacerbate the shuttle effect,while a lean electrolyte may lead to decreased Li-ion conductivity and reduced catalytic conversion efficiency,so achieving an appropriate electrolyte-to-sulfur ratio(E/S ratio)is essential for improving the battery cycling efficiency.A quasi-solid electrolyte(COF-SH@PVDF-HFP)with strong adsorption and high catalytic conversion was constructed for in situ covalent organic framework(COF)growth on highly polarized polyvinylidene fluoride-hexafluoropropylene(PVDF-HFP)fibers.COF-SH@PVDF-HFP enables efficient Li-ion conductivity with low-content liquid electrolyte and effectively suppresses the shuttle effect.The results based on in situ Fourier-transform infrared,in situ Raman,UV–Vis,X-ray photoelectron,and density functional theory calculations confirmed the high catalytic conversion of COF-SH layer containing sulfhydryl and imine groups for the lithium polysulfides.Lithium plating/stripping tests based on Li/COF-SH@PVDF-HFP/Li show excellent lithium compatibility(5 mAh cm^(-2) for 1400 h).The assembled Li-S battery exhibits excellent rate(2 C 688.7 mAh g^(-1))and cycle performance(at 2 C of 568.8 mAh g^(-1) with a capacity retention of 77.3%after 800 cycles).This is the first report to improve the cycling stability of quasi-solid-state Li-S batteries by reducing both the E/S ratio and the designing strategy of sulfhydryl-functionalized COF for quasi-solid electro-lytes.This process opens up the possibility of the high performance of solid-state Li-S batteries.
基金supports from National Natural Science Foundation of China(21938009,22308358,22208346,22078332)National Key Research and Development Program(2022YFC3902701)+2 种基金Ningxia Natural Science Foundation(2021AAC01002)the External Cooperation Program of BIC,Chinese Academy of Sciences(122111KYSB20190032)CAS Project for Young Scientists in Basic Research(YSBR-038)are gratefully acknowledged.
文摘NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer.Effects of alkalinity ranging from 0.38 to 0.55(n(Na_(2)O)/n(SiO_(2)))on the relative crystallinity,textural properties and crystallization kinetics were investigated.The results show that alkalinity exerts a nonmonotonic influence on the relative crystallinity and textural properties,which exhibit a maximum at the alkalinity of 0.43.The nucleation kinetics are studied by fitting the experimental data of relative crystallinity with the Gualtieri model.It is shown that the nucleation rate constant increases with increasing alkalinity,while the duration period of nucleation decreases with increasing alkalinity.For n(Na_(2)O)/n(SiO_(2))ratios ranging from 0.38 to 0.55,the as-synthesized NaY zeolites exhibit narrower crystal size distributions with the increase in alkalinity.The growth rates determined from the variations of average crystal size with time are 51.09,157.50,46.17 and 24.75 nm·h^(-1),respectively.It is found that the larger average crystal sizes at the alkalinity of 0.38 and 0.43 are attributed to the dominant role of crystal growth over nucleation.Furthermore,the combined action of prominent crystal growth and the longer duration periods of nucleation at the alkalinity of 0.38 and 0.43 results in broader crystal size distributions.The findings demonstrate that control of the properties of NaY zeolite and the crystallization kinetics can be achieved by conducting the crystallization process in an appropriate range of alkalinity of the reaction mixture.
基金supported by the National Natural Science Foundation of China (52202104)the China Postdoctoral Science Foundation (2021T140433,2020M683408)+6 种基金the Joint Funds of the Zhejiang Provincial Natural Science Foundation of China (LZY23B030002)the Quzhou Science and Technology Bureau Project (2021D006)the International Cooperation Projects of Sichuan Provincial Department of Science and Technology (2021YFH0126)the Fundamental Research Funds for the Central Universities (ZYGX2020ZB016)the Key Research and Development Program of Yunnan Province China (202103AA080019)the Yunnan Major Scientific and Technological Projects (202202AG050003)the Foundation of Key Laboratory of Advanced Technique&Preparation for Renewable Energy Materials,Ministry of Education,Yunnan Normal University (OF2022-04)。
文摘The practical application of lithium-sulfur(Li-S)batteries,as promising next-generation batteries,is hindered by their shuttle effect and the slow redox kinetics.Herein,a tungsten and molybdenum nitride heterostructure functionalized with hollow metal-organic framework-derived carbon(W_(2)N/Mo_(2)N)was proposed as the sulfur host.The hollow spherical structure provides storage space for sulfur,enhances electrical conductivity,and inhibits volume expansion.The metal atoms in the nitrides bonded with lithium polysulfides(Li PSs)through Lewis covalent bonds,enhancing the high catalytic activity of the nitrides and effectively reducing the energy barrier of Li PSs redox conversion.Moreover,the high intrinsic conductivity of nitrides and the ability of the heterostructure interface to accelerate electron/ion transport improved the Li+transmission.By leveraging the combined properties of strong adsorption and high catalytic activity,the sulfur host effectively inhibited the shuttle effect and accelerated the redox kinetics of Li PSs.High-efficiency Li+transmission,strong adsorption,and the efficient catalytic conversion activities of Li PSs in the heterostructure were experimentally and theoretically verified.The results indicate that the W_(2)N/Mo_(2)N cathode provides stable,and long-term cycling(over 2000 cycles)at 3 C with a low attenuation rate of 0.0196%per cycle.The design strategy of a twinborn nitride heterostructure thus provides a functionalized solution for advanced Li-S batteries.
文摘目的 探瘤Sp ECT/CT标准化摄取值(sta n d ard upta ke value,SUV)联合超声在预测甲状腺结节良恶性中的价值。方法选取2022年4月至2024年5月经超声诊断为非囊性、甲状腺显像诊断为“非热结节”的92例甲状腺结节患者,择期行甲状腺甲氧基异丁基异腈(^(99m)Tc-Ml BI)亲肿瘤显像及定量S P E CT/CT检查,采用定参数自动勾画方式分别勾画感兴趣区(ROI)获得SUV值,以病理结果为“金标准”。采用ROC曲线对SUV在对甲状腺结节良恶性进行评估时的灵敏度和特异度进行分析,获得诊断界值。采用配对χ^(2)检验比较分析定量SPECT/CT SUV值、超声及联合诊断对甲状腺结节良恶性的鉴别诊断效能。结果92例患者中甲状腺恶性结节32例,良性结节60例,甲状腺恶性组平均标准化摄取值(SUV mean)和最大标准化摄取值(SUVmax)高于良性组,差异有统计学意义;ROC曲线结果提示SUVmean、SUVmax的诊断界值、曲线下面积(AUC)分别为2.57g/mL、 0.840和5.17g/mL、0.892,SUVmax的诊断效能更高。SUVmax组、超声组及联合组诊断灵敏度分别为53.12%、75.00%、87.5%,特异度分别力88.33%、78.33%、83.33%,准确度分别为76.09%、77.17%、84.78%。配对χ^(2)检验结果表明,超声和SUVmax组诊断的准确性有显著性差异(χ^(2)=20.488,P<0.01),联合诊断的准确性优于SUVmax和超声(χ^(2)=46.142,P<0.01;χ^(2)=58.536,P<0.01)。ROC曲线结果显示三组的AUC分别为0.707、0.767、0.854,联合诊断效能最高。结论精准定量SPECT/CTSUVmax值尤其是与超声联合诊断可以在穿刺活检或手术确诊前提高甲状腺恶性结节的检出率和诊断效能,其单独鉴别诊断甲状腺结节良恶性的诊断界值为5.17g/m L。
