Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)acc...Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.展开更多
Series of heterogeneous interfacial engineered TiO2(C-TiO2) with controllable carbon content were facilely synthesized by incipient-wet impregnation using glucose and subsequent thermal carbonization. The obtained C-T...Series of heterogeneous interfacial engineered TiO2(C-TiO2) with controllable carbon content were facilely synthesized by incipient-wet impregnation using glucose and subsequent thermal carbonization. The obtained C-TiO2 were used as catalytic supports to load Pd nanoparticles for H2 O2 direct synthesis from H2 and O2. The as-prepared samples were systematically studied by transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), air isothermal microcalorimeter, temperature-programmed reduction of H2(H2-TPR), and so on. The catalytic results showed that H2 O2 productivity and H2O2 selectivity of Pd/C-TiO2 firstly rose with increasing carbon content and then declined. Pd/C-TiO2 catalyst with 1.89 wt% of carbon content showed the best catalytic performance that had 61.2% of selectivity and 2192 mmol H2O2/g Pd/h of productivity, which were significantly better than those of pristine Pd/TiO2(45.2% and 1827 mmol H2O2/g Pd/h). Various characterization results displayed that the carbon species were heterogeneously dispersed on TiO2 surface. Moreover, no obvious geometric transformation in supports and Pd nanoparticles were observed among different catalysts. The superficial hydrophobicity of Pd/C-TiO2 was gradually promoted with increasing carbon content, which led to the corresponding decrease in adsorption energy of H2O2 with catalysts. According to structure-performance relationship analyses, the heterogeneous interfacial engineering of carbon could maintain the interaction of Pd nanoparticles with TiO2 and simultaneously accelerate the H2O2 desorption. Both factors further determined the excellent H2O2 direct synthesis performance of Pd/C-TiO2.展开更多
The preparation process and properties of the thermally prepared Ti anodes coated with IrO2+Ta2O5 was studied. The structure and morphologies of the IrO2+Ta2O5 coatings were determined by XRD and SEM. Their electroche...The preparation process and properties of the thermally prepared Ti anodes coated with IrO2+Ta2O5 was studied. The structure and morphologies of the IrO2+Ta2O5 coatings were determined by XRD and SEM. Their electrochemical properties were studied by polarization curve and cyclic voltammetry. Trivalent chromium electroplating using Ti/IrO2+Ta2O5 anodes is carried out and the results were analyzed. Results show that this anode exhibits excellent electrochemical activity and stability in sulfate electrolysis. The electrocatalytic activity is determined not only by the content of IrO2 but also the structure and morphology of the anode coatings. The electroplating results indicats that Ti/IrO2+Ta2O5 anodes have excellent capabilities and merits in improving the stability of trivalent chromium electroplating in sulfate system.展开更多
New visible transparent, UV absorption, and high infrared reflection properties have been realized by depositing multilayer Si O2/Zn O: Al/Ce O2-Ti O2/Si O2 films onto glass substrates at low temperature by radio freq...New visible transparent, UV absorption, and high infrared reflection properties have been realized by depositing multilayer Si O2/Zn O: Al/Ce O2-Ti O2/Si O2 films onto glass substrates at low temperature by radio frequency magnetron sputtering. Optimum thickness of Si O2, Zn O: Al(ZAO) and Ce O2-Ti O2(CTO) films were designed with the aid of thin film design software. The degree of antireflection can be controlled by adjusting the thickness and refractive index. The outer Si O2 film can diminish the interference coloring and increase the transparency; the inner Si O2 film improves the adhesion of the coating on the glass substrate and prevents Ca2+, Na+ in the glass substrate from entering the ZAO film. The average transmittance in the visible light range increases by nearly 18%-20%, as compared to double layer ZAO/CTO films. And the films display high infrared reflection rate of above 75% in the wavelength range of 10-25 μm and good UV absorption(> 98%) properties. These systems are easy to produce on a large scale at low cost and exhibit high mechanical and chemical durability. The triple functional films with high UV absorption, antireflective and high infrared reflection rate will adapt to application in flat panel display and architectural coating glass, automotive glass, with diminishing light pollution as well as decreasing eye fatigue and increasing comfort.展开更多
The influence of an N2O plasma pre-treatment technique on characteristics of AlGaN/GaN high electron mobility transistor（HEMT） prepared by using a plasma-enhanced chemical vapor deposition（PECVD） system is present...The influence of an N2O plasma pre-treatment technique on characteristics of AlGaN/GaN high electron mobility transistor（HEMT） prepared by using a plasma-enhanced chemical vapor deposition（PECVD） system is presented.After the plasma treatment,the peak transconductance（gm） increases from 209 mS/mm to 293 mS/mm.Moreover,it is observed that the reverse gate leakage current is lowered by one order of magnitude and the drain current dispersion is improved in the plasma-treated device.From the analysis of frequency-dependent conductance,it can be seen that the trap state density（DT） and time constant（τT） of the N20-treated device are smaller than those of a non-treated device.The results indicate that the N2O plasma pre-pretreatment before the gate metal deposition could be a promising approach to enhancing the performance of the device.展开更多
The Li-rich layered oxides show a higher discharge capacity over 250 mAh/g and have been developed into a promising positive material for lithium ion batteries. A rare earth metal oxyfluoride YOF-coated Li[Lio.2Mno.54...The Li-rich layered oxides show a higher discharge capacity over 250 mAh/g and have been developed into a promising positive material for lithium ion batteries. A rare earth metal oxyfluoride YOF-coated Li[Lio.2Mno.54Ni0.13Co0.13]O2 composites have been synthesized by a simple wet chem- ical method. Crystal structure, micro-morphology and element valence of the pristine and YOF-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 materials are characterized by XRD, SEM, TEM, and XPS. The results indicate that all materials exhibit a typical layered structure, and are made up of small and homogenous parti- cles ranging from 100 nm to 200 nm. In addition, YOF layer with a thickness of approximately 3-8 nm is precisely coated on the surface of the Li[Li0.2Mn0.54Ni0.13Co0.13]02. Constant current charge/discharge tests at various current densities show that the electrochemical performance of 2 wt% YOF-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 has been improved significantly. 2 wt% YOF-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 delivers the highest discharge capacity of 250.4 mAh/g at 20 mA/g among all the samples, and capacity retention of 87% after 100 charge/discharge cycles at 200 mA/g while that of the pristine one is only 81.6%. The superior electrochemical performance of 2wt% YOF-coated sample is ascribed to YOF coating layer, which could not only reduce side reactions between the electrode and liquid electrolyte, but also promote lithium ion migration.展开更多
The co-precipitation derived LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 cathode material was modified by a coating layer of TiP_2O_7 through an ethanol-based process. The TiP_2O_7-coated LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 is charac...The co-precipitation derived LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 cathode material was modified by a coating layer of TiP_2O_7 through an ethanol-based process. The TiP_2O_7-coated LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 is characterized by Xray diffraction analysis, scanning electron microscopy and transmission electron microscopy to investigate the microstructure and morphology. The differential scanning calorimetry was employed to confirm the improved thermal stability. The electrochemical properties were evaluated by the constant-current charge/discharge tests. The TiP_2O_7 coating layer is effectively suppressing the structural degradation and ameliorating the surface status of LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 particles, and the intrinsic rhombohedral layered structure of TiP_2O_7-coated LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 was well maintained during the long-term cycling process, while the surface structure of pristine LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 was degraded from rhombohedral R3 m layered structure to cubic rock-salt structure. The charged state Ni^(4+) ions will easily transform into Ni^(2+) when the electrolytes oxidized at the interface of cathode/electrolytes and formed the cubic rock-salt NiO type structure, and the cubic rock-salt structure without electrochemical activity on the surface of LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 particles will finally accelerate capacity fading. The thermal stability and cyclic performances of the LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 electrode were remarkably improved by TiP_2O_7 coating, the total amount of heat release corresponding to the intensity of thermal runaway were 1075.5 and 964.6 J/g for pristine LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 and TiP_2O_7-coated LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 respectively, the pouch shaped full cells that employed TiP 2 O7-coated LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 as cathode were able to perform more than 2200 cycles at 25 ℃ and more than 1000 cycles at 45 ℃ before the capacity retention fading to 80%.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22479097)the Shanghai Science and Technology Committee(Grant No.23ZR1433000)the National High-Level Talent Program for Young Scholars,the Start-up Fund(F.S.)from Shanghai Jiao Tong University.
文摘Structural reconstruction of electrocatalysts plays a pivotal role in catalytic performances for CO_(2)reduction reaction(CO_(2)RR),whereas the behavior is by far superficially understood.Here,we report that CO_(2)accessibility results in a universal self-adaptive structural reconstruction from Cu_(2)O to Cu@CuxO composites,ending with feeding gas-dependent microstructures and catalytic performances.The CO_(2)-rich atmosphere favors reconstruction for CO_(2)RR,whereas the CO_(2)-deficient one prefers that for hydrogen evolution reaction.With the assistance of spectroscopic analysis and theoretical calculations,we uncover a CO_(2)-induced passivation behavior by identifying a reductionresistant but catalytic active Cu(I)-rich amorphous layer stabilized by*CO intermediates.Additionally,we find extra CO production is indispensable for the robust production of C2H4.An inverse correlation between durability and FECO/FEC2H4 is disclosed,suggesting that the selfstabilization process involving the absorption of*CO intermediates on Cu(I)sites is essential for durable electrolysis.Guided by this insight,we design hollow Cu_(2)O nanospheres for durable and selective CO_(2)RR electrolysis in producing C2H4.Our work recognizes the previously overlooked passivation reconstruction and self-stabilizing behavior and highlights the critical role of the local atmosphere in modulating reconstruction and catalytic processes.
基金supported by the National Natural Science Foundation of China(21878143,21476106,21838004)Joint Re-search Fund for Overseas Chinese Scholars and Scholars in Hong Kong and Macao Young Scholars(21729601)+1 种基金the fund of State Key Laboratory of Materials-Oriented Chemical Engineering(ZK201702)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)~~
文摘Series of heterogeneous interfacial engineered TiO2(C-TiO2) with controllable carbon content were facilely synthesized by incipient-wet impregnation using glucose and subsequent thermal carbonization. The obtained C-TiO2 were used as catalytic supports to load Pd nanoparticles for H2 O2 direct synthesis from H2 and O2. The as-prepared samples were systematically studied by transmission electron microscopy(TEM), X-ray photoelectron spectroscopy(XPS), air isothermal microcalorimeter, temperature-programmed reduction of H2(H2-TPR), and so on. The catalytic results showed that H2 O2 productivity and H2O2 selectivity of Pd/C-TiO2 firstly rose with increasing carbon content and then declined. Pd/C-TiO2 catalyst with 1.89 wt% of carbon content showed the best catalytic performance that had 61.2% of selectivity and 2192 mmol H2O2/g Pd/h of productivity, which were significantly better than those of pristine Pd/TiO2(45.2% and 1827 mmol H2O2/g Pd/h). Various characterization results displayed that the carbon species were heterogeneously dispersed on TiO2 surface. Moreover, no obvious geometric transformation in supports and Pd nanoparticles were observed among different catalysts. The superficial hydrophobicity of Pd/C-TiO2 was gradually promoted with increasing carbon content, which led to the corresponding decrease in adsorption energy of H2O2 with catalysts. According to structure-performance relationship analyses, the heterogeneous interfacial engineering of carbon could maintain the interaction of Pd nanoparticles with TiO2 and simultaneously accelerate the H2O2 desorption. Both factors further determined the excellent H2O2 direct synthesis performance of Pd/C-TiO2.
文摘The preparation process and properties of the thermally prepared Ti anodes coated with IrO2+Ta2O5 was studied. The structure and morphologies of the IrO2+Ta2O5 coatings were determined by XRD and SEM. Their electrochemical properties were studied by polarization curve and cyclic voltammetry. Trivalent chromium electroplating using Ti/IrO2+Ta2O5 anodes is carried out and the results were analyzed. Results show that this anode exhibits excellent electrochemical activity and stability in sulfate electrolysis. The electrocatalytic activity is determined not only by the content of IrO2 but also the structure and morphology of the anode coatings. The electroplating results indicats that Ti/IrO2+Ta2O5 anodes have excellent capabilities and merits in improving the stability of trivalent chromium electroplating in sulfate system.
基金Funded by the Natural Science Foundation of Hubei Province(No.2014CFB563)the key Technology Innovation Project of Hubei Province(No.2013AAA005)China Postdoctoral Science Foundation(Nos.2013T60752 and 2012M511689)
文摘New visible transparent, UV absorption, and high infrared reflection properties have been realized by depositing multilayer Si O2/Zn O: Al/Ce O2-Ti O2/Si O2 films onto glass substrates at low temperature by radio frequency magnetron sputtering. Optimum thickness of Si O2, Zn O: Al(ZAO) and Ce O2-Ti O2(CTO) films were designed with the aid of thin film design software. The degree of antireflection can be controlled by adjusting the thickness and refractive index. The outer Si O2 film can diminish the interference coloring and increase the transparency; the inner Si O2 film improves the adhesion of the coating on the glass substrate and prevents Ca2+, Na+ in the glass substrate from entering the ZAO film. The average transmittance in the visible light range increases by nearly 18%-20%, as compared to double layer ZAO/CTO films. And the films display high infrared reflection rate of above 75% in the wavelength range of 10-25 μm and good UV absorption(> 98%) properties. These systems are easy to produce on a large scale at low cost and exhibit high mechanical and chemical durability. The triple functional films with high UV absorption, antireflective and high infrared reflection rate will adapt to application in flat panel display and architectural coating glass, automotive glass, with diminishing light pollution as well as decreasing eye fatigue and increasing comfort.
基金supported by the National Natural Science Foundation of China(Grant No.61334002)the Opening Project of Science and Technology on Reliability Physics and Application Technology of Electronic Component Laboratory,China(Grant No.ZHD201206)
文摘The influence of an N2O plasma pre-treatment technique on characteristics of AlGaN/GaN high electron mobility transistor（HEMT） prepared by using a plasma-enhanced chemical vapor deposition（PECVD） system is presented.After the plasma treatment,the peak transconductance（gm） increases from 209 mS/mm to 293 mS/mm.Moreover,it is observed that the reverse gate leakage current is lowered by one order of magnitude and the drain current dispersion is improved in the plasma-treated device.From the analysis of frequency-dependent conductance,it can be seen that the trap state density（DT） and time constant（τT） of the N20-treated device are smaller than those of a non-treated device.The results indicate that the N2O plasma pre-pretreatment before the gate metal deposition could be a promising approach to enhancing the performance of the device.
基金financially supported by the National Basic Research Program of China(Grant no.2015CB251100)
文摘The Li-rich layered oxides show a higher discharge capacity over 250 mAh/g and have been developed into a promising positive material for lithium ion batteries. A rare earth metal oxyfluoride YOF-coated Li[Lio.2Mno.54Ni0.13Co0.13]O2 composites have been synthesized by a simple wet chem- ical method. Crystal structure, micro-morphology and element valence of the pristine and YOF-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 materials are characterized by XRD, SEM, TEM, and XPS. The results indicate that all materials exhibit a typical layered structure, and are made up of small and homogenous parti- cles ranging from 100 nm to 200 nm. In addition, YOF layer with a thickness of approximately 3-8 nm is precisely coated on the surface of the Li[Li0.2Mn0.54Ni0.13Co0.13]02. Constant current charge/discharge tests at various current densities show that the electrochemical performance of 2 wt% YOF-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 has been improved significantly. 2 wt% YOF-coated Li[Li0.2Mn0.54Ni0.13Co0.13]O2 delivers the highest discharge capacity of 250.4 mAh/g at 20 mA/g among all the samples, and capacity retention of 87% after 100 charge/discharge cycles at 200 mA/g while that of the pristine one is only 81.6%. The superior electrochemical performance of 2wt% YOF-coated sample is ascribed to YOF coating layer, which could not only reduce side reactions between the electrode and liquid electrolyte, but also promote lithium ion migration.
基金supported by the National Natural Science Foundation of China (No. 51372178)the Natural Science Foundation for Distinguished Young Scholars of Hubei Province of China (No. 2013CFA021)
文摘The co-precipitation derived LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 cathode material was modified by a coating layer of TiP_2O_7 through an ethanol-based process. The TiP_2O_7-coated LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 is characterized by Xray diffraction analysis, scanning electron microscopy and transmission electron microscopy to investigate the microstructure and morphology. The differential scanning calorimetry was employed to confirm the improved thermal stability. The electrochemical properties were evaluated by the constant-current charge/discharge tests. The TiP_2O_7 coating layer is effectively suppressing the structural degradation and ameliorating the surface status of LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 particles, and the intrinsic rhombohedral layered structure of TiP_2O_7-coated LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 was well maintained during the long-term cycling process, while the surface structure of pristine LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 was degraded from rhombohedral R3 m layered structure to cubic rock-salt structure. The charged state Ni^(4+) ions will easily transform into Ni^(2+) when the electrolytes oxidized at the interface of cathode/electrolytes and formed the cubic rock-salt NiO type structure, and the cubic rock-salt structure without electrochemical activity on the surface of LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 particles will finally accelerate capacity fading. The thermal stability and cyclic performances of the LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 electrode were remarkably improved by TiP_2O_7 coating, the total amount of heat release corresponding to the intensity of thermal runaway were 1075.5 and 964.6 J/g for pristine LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 and TiP_2O_7-coated LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 respectively, the pouch shaped full cells that employed TiP 2 O7-coated LiNi_(0.8)Co_(0.15)Al_(0.05)O_2 as cathode were able to perform more than 2200 cycles at 25 ℃ and more than 1000 cycles at 45 ℃ before the capacity retention fading to 80%.
