The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, l...The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron- transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H2-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H2 by Ni-modified TiO2, the formation of NiSx as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO2/Ni-NiSx photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO2 surface and the subsequent formation of NiSx on the Ni surface by a hydrothermal reaction method. It was found that the TiO2/Ni-NiSx photocatalysts exhibited enhanced photocatalytic H2-evolution activity. In particular, TiO2/Ni-NiSx(30%) showed the highest photocatalytic rate (223.74 μmol h.1), which was greater than those of TiO2, TiO2/Ni, and TiO2/NiSx by factors of 22.2, 8.0, and 2.2, respectively. The improved H2-evolution performance of TiO2/Ni-NiSx could be attributed to the excellent synergistic effect of Ni and NiSx, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO2 surface and NiSx serves as interfacial active sites to capture H+ ions from solution and promote the interfacial H2-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.展开更多
Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries,the severe capacity fading caused by consecutive reduction reaction...Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries,the severe capacity fading caused by consecutive reduction reactions on the aggressively reactive surface is inevitable given the scarcity of effective protecting layers.Herein,by introducing a flame-retardant localized high-concentration electrolyte with retentive solvation configuration and relatively weakened anion-coordination and non-solvating fluorinated ether,the rational solid electrolyte interphase characterized by well-balanced inorganic/organic components is tailored in situ.This effectively prevented solvents from excessively decomposing and simultaneously improved the resistance against K-ion transport.Consequently,the graphite anode retained a prolonged cycling capability of up to 1400 cycles(245 mA h g,remaining above 12 mon)with an excellent capacity retention of as high as 92.4%.This is superior to those of conventional and high-concentration electrolytes.Thus,the optimized electrolyte with moderate salt concentration is perfectly compatible with graphite,providing a potential application prospect for K-storage evolution.展开更多
Ru has recently been regarded as a promising catalyst for hydrogen oxidation reaction(HOR) and hydrogen evolution reaction(HER) due to its similar binding energy towards *H but lower price compared to Pt.Nevertheless,...Ru has recently been regarded as a promising catalyst for hydrogen oxidation reaction(HOR) and hydrogen evolution reaction(HER) due to its similar binding energy towards *H but lower price compared to Pt.Nevertheless, the quest of high-efficiency Ru-based catalysts for HOR and HER is driven by the current disadvantages including low activity and unsatisfactory stability. Herein, we have fabricated and engineered two-dimensional(2D) Ru-based snow-like nanosheets with Ru/Ru O2interface(Ru/Ru O2SNSs)via a post-annealing treatment. Detailed characterizations and theoretical calculations indicate that the interfacial synergy, which is dependent on the temperature for annealing, can alter the hydrogen binding energy(HBE) and hydroxide binding energy(OHBE), as a result of the enhanced HOR and HER performance. Impressively, the optimal Ru/RuO_(2) SNSs display a mass activity of 9.13 A mgRu^(–1) at an overpotential of 50 m V in 0.1 mol L^(–1) KOH for HOR, which is 65, 304, and 21 times higher than those of Ru SNSs(0.14 A mg_(Ru)^(–1)), RuO_(2) SNSs(0.03 A mg_(Ru)^(–1)), and commercial Pt/C(0.43 A mg_(Ru)^(–1)), respectively.Moreover, Ru/RuO_(2) SNSs display improved HER activity with a low overpotential of 20.2 m V for achieving10 m A cm^(-2)in 1 mol L^(–1)KOH. This work not only provides an efficient catalyst for HOR and HER, but also promotes fundamental research on the fabrication and modification of catalysts in heterogeneous catalysis.展开更多
The electrode/electrolyte interface plays a cri- tical role in the performance of a Li-ion battery. In view of the dynamic and complex nature of the interface, in situ research approaches can provide valuable informat...The electrode/electrolyte interface plays a cri- tical role in the performance of a Li-ion battery. In view of the dynamic and complex nature of the interface, in situ research approaches can provide valuable information of interfacial phenomena during battery operation. In situ scanning probe microscopy （SPM） is a powerful technique used for the interfacial investigation of the Li-ion batteries. The versatile SPM techniques and their various operation modes have been utilized to measure the morphology and other properties of the electrode interface at high resolu- tion. Herein, we discuss the related SPM techniques to study the topography, mechanics and electrochemistry re- search of electrodes. Recent progresses of in situ SPM research on the electrode/electrolyte interface are summa- rized. Finally, the outlook of the technique is discussed.展开更多
The dynamic behavior of the interface between few layer graphene(FLG) and tungsten metal tips under Joule heating has been studied by in-situ transmission electron microscopy(TEM) method. High-resolution and real-time...The dynamic behavior of the interface between few layer graphene(FLG) and tungsten metal tips under Joule heating has been studied by in-situ transmission electron microscopy(TEM) method. High-resolution and real-time observations show the tungsten tip ‘swallow' carbon atoms of the FLG and ‘spit' graphite shells at its surface. The tip was carbonized to tungsten carbide(WC, W_2 C and WC_x) after this process. A carbon diffusion mechanism has been proposed based on the diffusion of carbon atoms through the tungsten tip and separation from the surface of the tip. After Joule heating, the initial FLG-metal mechanical contact was transformed to FLG-WCx-W contact, which results in significant improvement on electrical conductivity at the interface.展开更多
基金supported by the National Natural Science Foundation of China(21477094)the Fundamental Research Funds for the Central Universities(WUT 2017IB002)~~
文摘The development of efficient photocatalytic H2-evolution materials requires both rapid electron transfer and an effective interfacial catalysis reaction for H2 production. In addition to the well-known noble metals, low-cost and earth-abundant non-noble metals can also act as electron- transfer mediators to modify photocatalysts. However, as almost all non-noble metals lack the interfacial catalytic active sites required for the H2-evolution reaction, the enhancement of the photocatalytic performance is limited. Therefore, the development of new interfacial active sites on metal-modified photocatalysts is of considerable importance. In this study, to enhance the photocatalytic evolution of H2 by Ni-modified TiO2, the formation of NiSx as interfacial active sites was promoted on the surface of Ni nanoparticles. Specifically, the co-modified TiO2/Ni-NiSx photocatalysts were prepared via a two-step process involving the photoinduced deposition of Ni on the TiO2 surface and the subsequent formation of NiSx on the Ni surface by a hydrothermal reaction method. It was found that the TiO2/Ni-NiSx photocatalysts exhibited enhanced photocatalytic H2-evolution activity. In particular, TiO2/Ni-NiSx(30%) showed the highest photocatalytic rate (223.74 μmol h.1), which was greater than those of TiO2, TiO2/Ni, and TiO2/NiSx by factors of 22.2, 8.0, and 2.2, respectively. The improved H2-evolution performance of TiO2/Ni-NiSx could be attributed to the excellent synergistic effect of Ni and NiSx, where Ni nanoparticles function as effective mediators to transfer electrons from the TiO2 surface and NiSx serves as interfacial active sites to capture H+ ions from solution and promote the interfacial H2-evolution reaction. The synergistic effect of the non-noble metal cocatalyst and the interfacial active sites may provide new insights for the design of highly efficient photocatalytic materials.
基金supported by the National Natural Science Foundation of China(91963118 and 52173246)Science Technology Program of Jilin Province(20200201066JC)the 111 Project(B13013)。
文摘Although graphite anodes operated with representative de/intercalation patterns at low potentials are considered highly desirable for K-ion batteries,the severe capacity fading caused by consecutive reduction reactions on the aggressively reactive surface is inevitable given the scarcity of effective protecting layers.Herein,by introducing a flame-retardant localized high-concentration electrolyte with retentive solvation configuration and relatively weakened anion-coordination and non-solvating fluorinated ether,the rational solid electrolyte interphase characterized by well-balanced inorganic/organic components is tailored in situ.This effectively prevented solvents from excessively decomposing and simultaneously improved the resistance against K-ion transport.Consequently,the graphite anode retained a prolonged cycling capability of up to 1400 cycles(245 mA h g,remaining above 12 mon)with an excellent capacity retention of as high as 92.4%.This is superior to those of conventional and high-concentration electrolytes.Thus,the optimized electrolyte with moderate salt concentration is perfectly compatible with graphite,providing a potential application prospect for K-storage evolution.
基金supported by the National Key R&D Program of China(2020YFB1505802)the Ministry of Science and Technology of China(2017YFA0208200,2016YFA0204100)+4 种基金the National Natural Science Foundation of China(22025108,U21A20327,and22121001)China Postdoctoral Science Foundation(2020M682083)Guangdong Provincial Natural Science Fund for Distinguished Young Scholars(2021B1515020081)Start-up Support from Xiamen University and the Guangzhou Key Laboratory of Low Dimensional Materials and Energy Storage Devices(20195010002)。
文摘Ru has recently been regarded as a promising catalyst for hydrogen oxidation reaction(HOR) and hydrogen evolution reaction(HER) due to its similar binding energy towards *H but lower price compared to Pt.Nevertheless, the quest of high-efficiency Ru-based catalysts for HOR and HER is driven by the current disadvantages including low activity and unsatisfactory stability. Herein, we have fabricated and engineered two-dimensional(2D) Ru-based snow-like nanosheets with Ru/Ru O2interface(Ru/Ru O2SNSs)via a post-annealing treatment. Detailed characterizations and theoretical calculations indicate that the interfacial synergy, which is dependent on the temperature for annealing, can alter the hydrogen binding energy(HBE) and hydroxide binding energy(OHBE), as a result of the enhanced HOR and HER performance. Impressively, the optimal Ru/RuO_(2) SNSs display a mass activity of 9.13 A mgRu^(–1) at an overpotential of 50 m V in 0.1 mol L^(–1) KOH for HOR, which is 65, 304, and 21 times higher than those of Ru SNSs(0.14 A mg_(Ru)^(–1)), RuO_(2) SNSs(0.03 A mg_(Ru)^(–1)), and commercial Pt/C(0.43 A mg_(Ru)^(–1)), respectively.Moreover, Ru/RuO_(2) SNSs display improved HER activity with a low overpotential of 20.2 m V for achieving10 m A cm^(-2)in 1 mol L^(–1)KOH. This work not only provides an efficient catalyst for HOR and HER, but also promotes fundamental research on the fabrication and modification of catalysts in heterogeneous catalysis.
基金supported by the National Basic Research Program of China(2011YQ03012415,2011CB932304 and2011CB808701)the National Natural Science Foundation of China(21127901,21373237,21433011)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDB12020100)
文摘The electrode/electrolyte interface plays a cri- tical role in the performance of a Li-ion battery. In view of the dynamic and complex nature of the interface, in situ research approaches can provide valuable information of interfacial phenomena during battery operation. In situ scanning probe microscopy （SPM） is a powerful technique used for the interfacial investigation of the Li-ion batteries. The versatile SPM techniques and their various operation modes have been utilized to measure the morphology and other properties of the electrode interface at high resolu- tion. Herein, we discuss the related SPM techniques to study the topography, mechanics and electrochemistry re- search of electrodes. Recent progresses of in situ SPM research on the electrode/electrolyte interface are summa- rized. Finally, the outlook of the technique is discussed.
基金supported by the Program from Ministry of Science and Technology(Grant Nos.2012CB933003,2013CB932600,2013CB934500&2013YQ16055107)the National Natural Science Foundation of China(Grant Nos.11474337,221322304,51172273&51421002)Strategic Priority Research Program B of the Chinese Academy of Sciences of China(Grant No.XDB07030100)
文摘The dynamic behavior of the interface between few layer graphene(FLG) and tungsten metal tips under Joule heating has been studied by in-situ transmission electron microscopy(TEM) method. High-resolution and real-time observations show the tungsten tip ‘swallow' carbon atoms of the FLG and ‘spit' graphite shells at its surface. The tip was carbonized to tungsten carbide(WC, W_2 C and WC_x) after this process. A carbon diffusion mechanism has been proposed based on the diffusion of carbon atoms through the tungsten tip and separation from the surface of the tip. After Joule heating, the initial FLG-metal mechanical contact was transformed to FLG-WCx-W contact, which results in significant improvement on electrical conductivity at the interface.
