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1.
Phosphorus‐modified tungsten nitride/reduced graphene oxide (P‐WN/rGO) is designed as a high‐efficient, low‐cost electrocatalyst for the hydrogen evolution reaction (HER). WN (ca. 3 nm in size) on rGO is first synthesized by using the H3[PO4(W3O9)4] cluster as a W source. Followed by phosphorization, the particle size increase slightly to about 4 nm with a P content of 2.52 at %. The interaction of P with rGO and WN results in an obvious increase of work function, being close to Pt metal. The P‐WN/rGO exhibits low onset overpotential of 46 mV, Tafel slope of 54 mV dec−1, and a large exchange current density of 0.35 mA cm−2 in acid media. It requires overpotential of only 85 mV at current density of 10 mA cm−2, while remaining good stability in accelerated durability testing. This work shows that the modification with a second anion is powerful way to design new catalysts for HER.  相似文献   

2.
The development of transition-metal-oxides (TMOs)-based bifunctional catalysts toward efficient overall water splitting through delicate control of composition and structure is a challenging task. Herein, the rational design and controllable fabrication of unique heterostructured inter-doped ruthenium–cobalt oxide [(Ru–Co)Ox] hollow nanosheet arrays on carbon cloth is reported. Benefiting from the desirable compositional and structural advantages of more exposed active sites, optimized electronic structure, and interfacial synergy effect, the (Ru–Co)Ox nanoarrays exhibited outstanding performance as a bifunctional catalyst. Particularly, the catalyst showed a remarkable hydrogen evolution reaction (HER) activity with an overpotential of 44.1 mV at 10 mA cm−2 and a small Tafel slope of 23.5 mV dec−1, as well as an excellent oxygen evolution reaction (OER) activity with an overpotential of 171.2 mV at 10 mA cm−2. As a result, a very low cell voltage of 1.488 V was needed at 10 mA cm−2 for alkaline overall water splitting.  相似文献   

3.
The development of inexpensive and efficient bifunctional electrocatalysts is significant for widespread practical applications of overall water splitting technology. Herein, a one-pot solvothermal method is used to prepare hollow porous MnFe2O4 spheres, which are grown on natural-abundant elm-money-derived biochar material to construct MnFe2O4/BC composite. When the overpotential is 156 mV for both the oxygen evolution reaction and the hydrogen evolution reaction, the current density reaches up to 10 mA cm−2, and its duration is 10 h. At 1.51 V, the overall water decomposition current density of 10 mA cm−2 can be obtained in 1 m KOH. This work proves that elm-money-derived biochar is a valid substrate for growing hollow porous spheres. MnFe2O4/BC give a promising general strategy for preparing the effective and stable bifunctional catalysis that can be expand to multiple transition metal oxide.  相似文献   

4.
Designing active and stable oxygen evolution reaction (OER) catalysts are vitally important to various energy conversion devices. Herein, we introduce elements Ni and Mn into (Co)tet(Co2)octO4 nanosheets (NSs) at fixed geometrical sites, including Mnoct, Nioct, and Nitet, to optimize the initial geometrical structure and modulate the CoCo2O4 surface from oxygen-excess to oxygen-deficiency. The pristine (Ni,Mn)-(Co)tet(Co2)octO4 NSs shows excellent OER activity with an overpotential of 281.6 mV at a current density of 10 mA cm−2. Moreover, without damaging their initial activity, the activated (Act)-(Ni,Mn)-(Co)tet(Co2)octO4 NSs after surface reconstruction exhibit long-term stability of 100 h under 10 mA cm−2, 50 mA cm−2, or even 100 mA cm−2. The optimal balance between electroactivity and stability leads to remarkable OER performances, providing a pivotal guideline for designing ideal electrocatalysts and inspiring more works to focus on the dynamic change of each occupation site component.  相似文献   

5.

For more sustainability and marketing of microbial fuel cells (MFCs) in wastewater treatment, the sluggish kinetics of cathode oxygen reduction reaction (ORR) and platinum scarcity (with its high cost) should be swept away. So, this work aimed to synthesize metal ferrite (MFe2O4; M = Mn, Cu, and Ni) -based activated carbon composites as inexpensive ORR cathode catalysts. The composites were synthesized using a facile modified co-precipitation approach with low-thermal treatment and labeled as MnFe2O4/AC, CuFe2O4/AC, and NiFe2O4/AC. The as-synthesized catalysts are physicochemically characterized by X-ray diffraction (XRD), Raman spectroscopy, Fourier transform infrared microscopy (FTIR), Barrett-Joyner-Halenda (BJH), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), and electron spin resonance (ESR). The electrochemical catalytic performance toward ORR was studied in a phosphate buffer solution (PBS) at neutral media via cyclic voltammetry (CV) and linear sweep voltammetry (LSV). MnFe2O4/AC has the highest onset potential (Eonset) value of − 0.223 V compared to CuFe2O4/AC (− 0.280 V) and NiFe2O4/AC (− 0.270 V). MnFe2O4/AC also has the highest kinetic current density (jK) and lowest Tafel slope (− 5 mA cm−2 and − 330 mV dec−1) compared to CuFe2O4/AC (− 3.05 mA cm−2 and − 577 mV dec−1) and NiFe2O4/AC (− 2.67 mA cm−2 and − 414 mV dec−1). The ORR catalyzed by MnFe2O4/AC at pH = 7 proceeds via a 4e -kinetic pathway. The ESR is in good agreement with the electrochemical analysis due to the highest ∆Hppvalue for MnFe2O4/AC compared to CuFe2O4/AC and NiFe2O4/AC. Thus, MnFe2O4/AC is suggested as a promising alternative to Pt- electrocatalyst cathode for MFCs at neutral conditions.

Graphical Abstract
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6.
将镍铁金属配位聚合物前驱体在惰性气氛下热分解制备了富氮洋葱碳(ONC)包覆的Ni/Ni Fe_2O_4多孔纳米棒复合析氧电催化剂,与Ni@ONC,Ni Fe_2O_4材料及传统Ru O_2催化剂相比,得益于这种富氮洋葱碳包覆的Ni/Ni Fe_2O_4一维多孔纳米异质结构,Ni/Ni Fe_2O_4@ONC材料拥有更优异的导电性能和更大的电化学活性面积(0.149 m F),因而表现出更优异的析氧电催化性能。Ni/Ni Fe_2O_4@ONC纳米棒在1 mol·L~(-1) KOH溶液中,10 m A·cm-2下的析氧过电位仅为299 m V,塔菲尔斜率为73 m V·dec-1,展现出优异的析氧稳定性能。  相似文献   

7.
Transition-metal oxides as electrocatalysts for the oxygen evolution reaction (OER) provide a promising route to face the energy and environmental crisis issues. Although palmeirite oxide A2Mo3O8 as OER catalyst has been explored, the correlation between its active sites (tetrahedral or octahedral) and OER performance has been elusive. Now, magnetic Co2Mo3O8@NC-800 composed of highly crystallized Co2Mo3O8 nanosheets and ultrathin N-rich carbon layer is shown to be an efficient OER catalyst. The catalyst exhibits favorable performance with an overpotential of 331 mV@10 mA cm−2 and 422 mV@40 mA cm−2, and a full water-splitting electrolyzer with it as anode catalyst shows a cell voltage of 1.67 V@10 mA cm−2 in alkaline. Combined HAADFSTEM, magnetic, and computational results show that factors influencing the OER performance can be attributed to the tetrahedral Co sites (high spin, t23e4), which improve the OER kinetics of rate-determining step to form *OOH.  相似文献   

8.
Phosphorus‐modified tungsten nitride/reduced graphene oxide (P‐WN/rGO) is designed as a high‐efficient, low‐cost electrocatalyst for the hydrogen evolution reaction (HER). WN (ca. 3 nm in size) on rGO is first synthesized by using the H3[PO4(W3O9)4] cluster as a W source. Followed by phosphorization, the particle size increase slightly to about 4 nm with a P content of 2.52 at %. The interaction of P with rGO and WN results in an obvious increase of work function, being close to Pt metal. The P‐WN/rGO exhibits low onset overpotential of 46 mV, Tafel slope of 54 mV dec?1, and a large exchange current density of 0.35 mA cm?2 in acid media. It requires overpotential of only 85 mV at current density of 10 mA cm?2, while remaining good stability in accelerated durability testing. This work shows that the modification with a second anion is powerful way to design new catalysts for HER.  相似文献   

9.
《化学:亚洲杂志》2017,12(22):2956-2961
Developing efficient non‐noble metal and earth‐abundant electrocatalysts with tunable microstructures for overall water splitting is critical to promote clean energy technologies for a hydrogen economy. Herein, novel three‐dimensional (3D) flower‐like Ni2P composed of mesoporous nanoplates with controllable morphology and high surface area was prepared by a hydrothermal method and low‐temperature phosphidation as efficient electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER). Compared with the urchin‐like Nix Py , the 3D flower‐like Ni2P with a diameter of 5 μm presented an efficient and stable catalytic performance in 0.5 m H2SO4, with a small Tafel slope of 79 mV dec−1 and an overpotential of about 240 mV at a current density of 10 mA cm−2 with a mass loading density of 0.283 mg cm−2. In addition, the catalyst also exhibited a remarkable performance for the OER in 1.0 m KOH electrolyte, with an overpotential of 320 mV to reach a current density of 10 mA cm−2 and a small Tafel slope of 72 mV dec−1. The excellent catalytic performance of the as‐prepared Ni2P may be ascribed to its novel 3D morphology with unique mesoporous structure.  相似文献   

10.
In this study, catalytic performance of nanoferrites NiFe2O4 and Ni0.3Zn0.7Fe2O4 is reported. Nickel–ferrite and mixed nickel–zinc ferrite were successfully synthesized by combustion reaction using a conical reactor with production of 10 g per batch. Crystallinity and purity or quantitative analysis of the catalyst were checked by using X-ray diffraction and energy dispersive X-ray analysis. Surface chemistry was examined via Fourier transform infrared (FTIR) analysis; N2 physisorption at 77 K was conducted to obtain textural properties of the catalyst; a thermogravimetric analysis, a scanning electron microscope and a transmission electron microscopy were used to check the thermal stability and morphology of the catalyst, respectively. The catalysts were used to convert soybean oil into biodiesel in a batch mode and the reaction mixture was analyzed using a pre-calibrated gas chromatograph (GC). The presence of a single-phase spinel structure in the synthesized nanoparticles was confirmed by the XRD results. The Ni0.3Zn0.7Fe2O4 had a lower surface area value of 71.5 m2g−1 and higher saturation magnetization value of 31.50 emu/g than sample NiFe2O4 which had 87.6 m2g−1 and 17.85 emu/g, respectively. Biodiesel yield of 94% was obtained with Ni0.3Zn0.7Fe2O4 and 49% was obtained with NiFe2O4. Better performance of Ni0.3Zn0.7Fe2O4 when compared to that of NiFe2O4 could be attributed to higher acidity of the former. Findings from this study suggest that the development of nickel-zinc ferrite nanoparticles as magnetic heterogeneous catalysts could provide an environmentally friendly platform for biodiesel production.  相似文献   

11.
A new magnetic metal–organic framework (MOF), namely, NiFe2O4@SiO2@Cu3(BTC)2, was synthesized via an in situ method using Fe(NO3)3, Ni(NO3)2, CuN2O6, TEOS, (3-aminopropyl)triethoxysilane, and benzene-1,3,5-tricarboxylic acid. Three different samples were fabricated according to a formula; xNiFe2O4@(100 − x)SiO2@Cu3(BTC)2, where x = 10, 30, and 50. The integration of the intrinsic characteristic of Cu3(BTC)2 as an MOF with strong magnetic properties of NiFe2O4 could lead to an exquisite material with specific behaviors. X-ray diffraction (XRD), Fourier transform infrared (FTIR), scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET), diffuse reflectance spectroscopy (DRS), photoluminescence (PL), vibrating sample magnetometer (VSM), transmission electron microscopy (TEM), and simulated thermal analyzer (STA) were utilized to characterize the mentioned samples. Results approved that the synthesized compounds were composed of SiO2 and Cu-MOF and NiFe2O4 crystalline phases with rod-like morphology. The similarity between the morphology of the synthesized samples and Cu-MOF approved that an appropriate fabrication method has been selected. This fact led to observe mesoporous composites with 38–90 m2 g−1 specific surface area. PL spectroscopy confirmed the near bandgap emission, ligand-to-metal charge transfer, and metal-to-ligand charge transfer. Although all the samples had magnetic hysteresis, the highest magnetization was seen in the 50NiFe2O4@SiO2@Cu3(BTC)2 sample. This composite compound with a magnetization value of 2 emu g−1 at 8000 Oe and a specific surface area of 90 m2 g−1 could be classified as a magnetic MOF (MMOF). STA results suggested that 400°C is the highest operating temperature for this compound.  相似文献   

12.
《Electroanalysis》2017,29(12):2698-2707
A cholesterol biosensor based on cholesterol oxidase‐poly(diallyldimethylammonium chloride)‐carbon nanotubes‐nickel ferrite nanoparticles (ChOx‐PDDA‐CNTs‐NiFe2O4NPs) solution is easily fabricated by using a single dropping step on a glassy carbon electrode (GCE) surface. This technique is an alternative way to reduce complexity, cost and time to produce the biosensor. The uniformly dispersed materials on the electrode surface enhance the catalytic reaction of cholesterol oxidase and electron transfer from the oxidation of hydrogen peroxide in the system. The nickel ferrite nanoparticles were synthesized by co‐precipitation and calcination at various temperatures. These nanoparticles were then characterized using field emission scanning electron microscopy (FE‐SEM), energy‐dispersive X‐ray spectroscopy (EDX), Fourier transform infrared spectroscopy (FTIR), cyclic voltammetry (CV) and X‐ray diffraction (XRD). The synthesized material calcined at 700 °C was well defined and presented the octahedral metal stretching with cubic NiFe2O4NPs phase. In cyclic voltammetric study, the ChOx‐PDDA‐CNTs‐NiFe2O4NPs/GCE showed 0.43 s−1 charge transfer rate constant (K s), 7.79×10−6 cm2 s−1 diffusion coefficient value (D ), 0.13 mm2 electroactive surface area (A e) and 3.58×10−8 mol cm−2 surface concentration ( ). This modified electrode exhibits stability in term of percent relative standard deviation (%RSD=0.62 %, n=10), reproducibility (%RSD=0.81, n=10), high sensitivity (25.76 nA per mg L−1 cm−2), linearity from 1 to 5,000 mg L−1 (R2=0.998) with a low detection limit (0.50 mg L−1). Its Michaelis‐Menten constant (K m) was 0.14 mM with 0.92 μA maximum current (I max) and demonstrated good selectivity without the effects of electroactive species such as ascorbic acid, glucose and uric acid. The cholesterol biosensor was successfully applied to determine cholesterol levels in human blood samples, showing promise due to its simplicity and availability.  相似文献   

13.
《化学:亚洲杂志》2018,13(18):2700-2707
The relationship between controllable morphology and electrocatalytic activity of Co3O4 and CoSe2 for the oxygen evolution reaction (OER) was explored in alkaline medium. Based on the time‐dependent growth process of cobalt precursors, 1D Co3O4 nanorods and 2D Co3O4 nanosheets were successfully synthesized through a facile hydrothermal process at 180 °C under different reaction times, followed by calcination at 300 °C for 2 h. Subsequently, 1D and 2D CoSe2 nanostructures were derived by selenization of Co3O4, which achieved the controllable synthesis of CoSe2 without templating agents. By comparing the electrocatalytic behavior of these cobalt‐based catalysts in 1 m KOH electrolyte toward the OER, both 2D Co3O4 and 2D CoSe2 nanocrystals have lower overpotentials and better electrocatalytic stability than that of 1D nanostructures. The 2D CoSe2 nanosheets require overpotentials of 372 mV to reach a current density of 50 mA cm−2 with a small Tafel slope of 74 mV dec−1. A systematic contrast of the electrocatalytic performances for the OER increase in the order: 1D Co3O4<2D Co3O4<1D CoSe2<2D CoSe2. This work provides fundamental insights into the morphology–performance relationships of both Co3O4 and CoSe2, which were synthesized through the same approach, providing a solid guide for designing OER catalysts.  相似文献   

14.
Hydrogen energy is considered as one of the ideal clean energies for solving the energy shortage and environmental issues, and developing highly efficient electrocatalysts for overall water splitting to produce hydrogen is still a huge challenge. Herein, for the first time, Ru-doped Cu2+1O vertically arranged nanotube arrays in situ grown on Cu foam (Ru/Cu2+1O NT/CuF) are reported and further investigated for their catalytic properties for overall water splitting. The Ru/Cu2+1O NT/CuF presents ultrahigh catalytic activities for both the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) in alkaline conditions, and it exhibits a small overpotential of 32 mV at 10 mA cm−2 in the HER, and only needs 210 mV overpotential to achieve a current density of 10 mA cm−2 in the OER. Importantly, the alkaline electrolyzer using Ru/Cu2+1O NT/CuF as a bifunctional electrocatalyst only needs 1.53 V voltage to deliver a current density of 10 mA cm−2, which is much lower than the benchmark of IrO2(+)/Pt(−) counterpart (1.64 V at 10 mA cm−2). The excellent performance of the Ru/Cu2+1O NT/CuF catalyst is attributed to its high conductive substrate and special Ru-doped nanotube structure, which provides a high electrochemical active surface area and 3D gas diffusion channel.  相似文献   

15.
The development of high-efficiency, low-cost, and earth-abundant electrocatalysts for overall water splitting remains a challenge. In this work, Ni-modified MoS2 hybrid catalysts are grown on carbon cloth (Ni-Mo-S@CC) through a one-step hydrothermal treatment. The optimized Ni-Mo-S@CC catalyst shows excellent hydrogen evolution reaction (HER) activity with a low overpotential of 168 mV at a current density of 10 mA cm−2 in 1.0 m KOH, which is lower than those of Ni-Mo-S@CC (1:1), Ni-Mo-S@CC (3:1), and pure MoS2. Significantly, the Ni-Mo-S@CC hybrid catalyst also displays outstanding oxygen evolution reaction (OER) activity with a low overpotential of 320 mV at a current density of 10 mA cm−2, and remarkable long-term stability for 30 h at a constant current density of 10 mA cm−2. Experimental results and theoretical analysis based on density functional theory demonstrate that the excellent electrocatalytic performance can be attributed mainly to the remarkable conductivity, abundant active sites, and synergistic effect of the Ni-doped MoS2. This work sheds light on a unique strategy for the design of high-performance and stable electrocatalysts for water-splitting electrolyzers.  相似文献   

16.
Despite the fact that many strategies have been developed to improve the efficiency of the oxygen evolution reaction (OER), the precise modulation of the surface electronic properties of catalysts to improve their catalytic activity is still challenging. Herein, we demonstrate that the surface active electron density of Co3O4 can be effectively regulated by an argon-ion irradiation method. X-ray photoelectron and synchrotron x-ray absorption spectroscopy, UV photoelectron spectrometry, and DFT calculations show that the surface active electron density band center of Co3O4 has been upshifted, leading to a significantly enhanced absorption capability of the oxo group. The optimized Co3O4-based catalysts exhibit an excellent overpotential of 260 mV at 10 mA cm−2 and Tafel slope of 54 mV dec−1, superior to the capability of the benchmark RuO2, representing one of the best Co-based OER catalysts. This approach could guide the future rational design and discovery of ideal electrocatalysts.  相似文献   

17.
To avoid an enormous energy crisis in the not-too-distant future, it be emergent to establish high-performance energy storage devices such as supercapacitors. For this purpose, a three-dimensional (3D) heterostructure of Co3O4 and Co3S4 on nickel foam (NF) that is covered by reduced graphene oxide (rGO) has been prepared by following a facile multistep method. At first, rGO nanosheets are deposited on NF under mild hydrothermal conditions to increase the surface area. Subsequently, nanowalls of cobalt oxide are electro-deposited on rGO/Ni foam by applying cyclic-voltammetry (CV) under optimized conditions. Finally, for the synthesis of Co3O4@Co3S4 nanocomposite, the nanostructure of Co3S4 was fabricated from Co3O4 nanowalls on rGO/NF by following an ordinary hydrothermal process through the sulfurization for the electrochemical application. The samples are characterized by using X-ray diffraction (XRD) and scanning electron microscopy (SEM). The obtained sample delivers a high capacitance of 13.34 F cm−2 (5651.24 F g−1) at a current density of 6 mA cm−2 compared to the Co3O4/rGO/NF electrode with a capacitance of 3.06 F cm−2 (1230.77 F g−1) at the same current density. The proposed electrode illustrates the superior electrochemical performance such as excellent specific energy density of 85.68 W h Kg−1, specific power density of 6048.03 W kg−1 and a superior cycling performance (86% after 1000 charge/discharge cycles at a scan rate of 5 mV s−1). Finally, by using Co3O4 @Co3S4/rGO/NF and the activated carbon-based electrode as positive and negative electrodes, respectively, an asymmetric supercapacitor (ASC) device was assembled. The fabricated ASC provides an appropriate specific capacitance of 79.15 mF cm−2 at the applied current density of 1 mA cm−2, and delivered an energy density of 0.143 Wh kg−1 at the power density of 5.42 W kg−1.  相似文献   

18.
Nano-sized nickel ferrite (NiFe2O4) and cobalt ferrite particles (CoFe2O4) were successfully synthesized using a hydrothermal method. Techniques of X-ray diffraction, scanning electron microscope, Fourier transform infrared spectrometer, energy dispersive X-ray spectroscopy, vibrating sample magnetometer and transmission electron microscope have been used to characterize and study the as-synthesized NiFe2O4 and CoFe2O4 products. The results showed that the average size of the nickel and cobalt ferrite nanoparticles is smaller than 10 and 100 nm, respectively. The results of magnetic measurement showed that the synthesized NiFe2O4 and CoFe2O4 nanoparticles were superparamagnetic and soft ferromagnetic materials, respectively. Study of adsorption behavior showed that these nanoparticles can act as a good adsorbent for removing Pb2+.  相似文献   

19.
《Electroanalysis》2017,29(5):1481-1489
Polymorphs of Manganese di oxide (MnO2) such as alpha (α), beta (β), gamma (γ), epsilon (ϵ), and MnOOH type materials were prepared via hydrothermal approach under different conditions. The samples were characterized by XRD, FESEM, FT‐IR, Raman and BET analysis. Cyclic voltammetry (CV) analysis confirm that α ‐ MnO2 shows better electro‐catalytic ability. Amperometry sensing of hydrogen peroxide (H2O2) was carried out by varying applied potential value with the polymorphs of MnO2. Compared with the other phases of MnO2, α ‐ MnO2 shows high linear range up to 20μM. The calculated sensitivity value for H2O2 sensing of different phases is in the order of α ‐ MnO2, β ‐ MnO2, ϵ ‐ MnO2, γ ‐ MnO2, MnOOH and found to be 0.094 mA μM−1 cm−2 > 0.072 mA μM−1 cm−2 > 0.07 mA μM−1 cm−2 > 0.03 mA μM−1 cm−2 > 0.01 mA μM−1 cm−2 respectively. All the characterization results reveal that crystalline phase plays a vital role in electrochemical behavior rather than crystalline size, morphology, surface charge, surface area.  相似文献   

20.
Combining the self-sacrifice of a highly crystalline substance to design a multistep chain reaction towards ultrathin active-layer construction for high-performance water splitting with atmospheric-temperature conditions and an environmentally benign aqueous environment is extremely intriguing and full of challenges. Here, taking cobalt carbonate hydroxides (CCHs) as the initial crystalline material, we choose the Lewis acid metal salt of Fe(NO3)3 to induce an aqueous-phase chain reaction generating free CO32− ions with subsequent instant FeCO3 hydrolysis. The resultant ultrathin (∼5 nm) amorphous Fe-based hydroxide layer on CCH results in considerable activity in catalyzing the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER), yielding 10/50 mA ⋅ cm−2 at overpotentials of 230/266.5 mV for OER and 72.5/197.5 mV for HER. The catalysts can operate constantly in 1.0 M KOH over 48 and 45 h for the OER and HER, respectively. For bifunctional catalysis for alkaline electrolyzer assembly, a cell voltage as low as 1.53 V was necessary to yield 10 mA cm−2 (1.7 V at 50 mA cm−2). This work rationally builds high-efficiency electrochemical bifunctional water-splitting catalysts and offers a trial in establishing a controllable nanolevel ultrathin lattice disorder layer through an atmospheric-temperature chemical route.  相似文献   

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