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1.
Cost-effective oxygen evolution reaction (OER) electrocatalysts play a key role in electrocatalytic water splitting process. Here, a facile and scalable strategy was applied to synthesize the bimetallic metal-organic frameworks (MOFs) with high OER activity, and the effects of AC magnetic field on OER was also investigated. Results shows that the bimetallic MOFs (Co0.4Ni0.6-MOF-74) exhibited a three-dimensional flower-like morphology, and possessed a higher BET specific area of 905.39 m2 g?1 as well as a smaller median pore size of 0.49 nm as compared to single metal MOFs; It owned a lowest overpotential of 314 mV at 10 mA cm?2 and Tafel slope of 79.39 mV dec?1, both are much lower than these of single metal MOFs, being due to the high specific area and more active sites derived from the distorted crystal structure; When AC magnetic field strength equaled to 5.50 mT, overpotential at 10 mA cm?2 for Co0.4Ni0.6-MOF-74 reached minimum value of 201 mV, reduced by about 36% as compared to that without magnetic field, indicated that AC magnetic field could greatly improve OER process. These improvements resulted from the spin polarization effect, magnetohydrodynamic (MHD) convection and improved active point temperature.  相似文献   

2.
Developing greatly efficient and steady non-noble metal bifunctional electrocatalyst is of great significance for reducing the energy consumption. In this work, we found that the construction of hierarchical nanostructures was an effective strategy to improve the catalytic performance of bimetallic transition-metal phosphide (NiCoP). Herein, we successfully synthesized the Ni1.5Co1.5P catalyst with porous nanosheet self-assembled microflowers (MFs) structure by sequential solvothermal, annealing and phosphorization treatment, and then adjusted the morphology of the MFs by changing the Ni/Co molar ratio to optimize its electronic structure and increase the exposed active sites, thereby improving catalytic activity of the catalyst. Specifically, the Ni1.5Co1.5P/MFs only required overpotentials of 141 mV and 314 mV to reach a current density of 10 mA cm−2 toward HER and OER, respectively. Impressively, during the continuous 12 h chronoamperometry measurement, the Ni1.5Co1.5P/MFs displayed good durability. In conclusion, this study provided a feasible strategy to explore and prepare low-cost non-noble metal bifunctional electrocatalysts.  相似文献   

3.
Advances in electrochemical interfaces have greatly facilitated the development of new energy systems that can replace traditional fossil fuels. Oxygen evolution reaction (OER) is the core reaction in the new energy conversion system to produce hydrogen. Here, nanorods structure of Mn3O4/Co9S8–Ni3S2/NF-4 was designed and assembled. The Mn3O4 has served as an appropriate matrix to build a composite structure with Co9S8–Ni3S2 to enhance the stability of catalyst. And the introduction of Mn regulated the electronic structure of Ni and Co, which increased the OER activity of matericals. Further characterization and electrochemical testing have suggested that between polymetallic can effectively optimize conductivity and enhance reaction kinetics. Mn3O4/Co9S8–Ni3S2/NF-4 can achieve overpotential of 188 mV at the current density of 10 mA cm?2 in alkaline solution, with small Tafel slope of 43.2 mV dec?1 and satisfactory stability of 30 h at 10 mA cm?2. This work may show a feasible reference in the design of high-efficient OER catalysts.  相似文献   

4.
Constructing high-efficient and nonprecious electrocatalysts is of primary importance for improving the efficiency of water splitting. Herein, a novel sunflower plate-like NiFe2O4/CoNi–S nanosheet heterostructure was fabricated via facile hydrothermal and electrodeposition methods. The as-fabricated NiFe2O4/CoNi–S heterostructure array exhibits remarkable bifunctional catalytic activity and stability toward oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) in alkaline media. It presents a small overpotential of 219 mV and 149 mV for OER and HER, respectively, to produce a current density of 10 mA cm?2. More significantly, when the obtained electrodes are used as both the cathode and anode in an electrolyzer, a voltage of 1.57 V is gained at 10 mA cm?2, with superior stability for 72 h. Such outstanding properties are ascribed to: the 3D porous network structure, which exposes more active sites and accelerates mass transfer and gas bubble emission; the high conductivity of CoNi–S, which provides faster charge transport and thus promotes the electrocatalytic reaction of the composites; and the effective interface engineering between NiFe2O4 (excellent performance for OER) and CoNi–S (high activity for HER), which leads to a shorter transport pathway and thus expedites electron transfer. This work provides a new strategy for designing efficient and inexpensive electrocatalysts for water splitting.  相似文献   

5.
A phytic acid-derived Co2-xNixP2O7-C/RGO composite was designed and facilely synthesized, in which phytic acid acted as both a phosphoric source and carbon source. Both carbon derived from phytic acid and reduced graphene oxide (RGO) in composite, enhanced the conductivity and thus improve its electrocatalytical capability. As-synthesized Co1.22Ni0.78P2O7-C/RGO composite exhibited excellent oxygen evolution reaction (OER) catalytic performances: At the current density of 10 mA cm−2, only a low overpotential of 283 mV and a small Tafel slope of 51 mV dec−1 were observed. Good OER catalytic performance was retained even after 10 h continuously running at a constant voltage, which is even comparable to those of first-rate noble metal catalyst RuO2. In addition, the performances of Co2-xNixP2O7-C/RGO catalysts were also strongly dependent on Ni content.  相似文献   

6.
Tuning nickel-based catalyst activity and understanding electrolyte and ionomer interaction for oxygen evolution reaction (OER) is crucial to improve anion exchange membrane (AEM) water electrolyzers. Herein, an investigation of multimetallic Ni0.6Co0.2Fe0.2 OER activity, coupled with in-situ Raman spectroscopy to track dynamic structure changes, was carried out and compared to other Ni catalysts. The effect of KOH concentration, KOH purity, ionomer type, and electrolyte with organic cations was evaluated. The Ni0.6Co0.2Fe0.2 catalyst achieved 10 mA/cm2 at 260 mV overpotential with stability over 50 h and 5000 cycles in 1 M KOH. In-situ Raman spectroscopy showed that Ni0.6Co0.2Fe0.2 activity originates from promoting Ni(OH)2/NiOOH transformation at low potentials compared to bi- and mono-metallic nickel-based catalysts. Fumion anion ionomer in the catalyst inks led to a lower OER activity than catalysts with inks containing Nafion ionomer. The OER activity of Ni0.6Co0.2Fe0.2 is adversely influenced in the presence of fumion anion ionomer and benzyltrimethylammonium hydroxide (BTMAOH) with possible phenyl oxidation under applied high anodic potentials. The alkaline AEM water electrolyzer circulating 1 M KOH electrolyte, with a Pt/C cathode and a Ni0.6Co0.2Fe0.2 anode, achieved 1.5 A/cm2 at 2 V.  相似文献   

7.
Synthesizing efficient and affordable electrocatalysts for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) remains a crucial problem on the way to practical applications for producing clean H2 fuel. Herein, high-efficiency and stable transition metal based electrocatalysts Ni0.85Se-1, Ni0.85Se-2 and Ni0.85Se-3 materials with different morphological characteristics were derived via a one-step hydrothermal route using the Ni(OH)2 and metal-organic framework (Ni-BDC and Ni-BTC) as precursors, respectively. The results showed that Ni0.85Se-2 exhibited excellent electrocatalytic activity. Subsequently, introducing carbon nanomaterials (RGO and CNTs) to form Ni0.85Se/RGO/CNTs nanocomposite material further improves the catalytic activity owing to high conductivity. The resulting Ni0.85Se/RGO/CNTs nanocomposites electrocatalyst showed a low overpotential of 232 mV and 165 mV and a low Tafel slope of 64 mV dec?1 and 98 mV dec?1 when the current density was 10 mA cm?2 for OER and HER, respectively. In addition, the Ni0.85Se/RGO/CNTs nanocomposites were used as an anode and cathode of the water electrolysis device and the overall water splitting performance was investigated. The results show just a voltage of 1.59 V was required when the current density was 10 mA cm?2 and good overall water splitting stability for 20 h. The outstanding electrocatalytic performance of Ni0.85Se/RGO/CNTs is mostly due to its noticeable porous structure, the high conductivity and the large surface area that came from RGO and CNTs.  相似文献   

8.
Reasonable design and preparation of non-noble metal electrocatalysts with predominant catalytic activity and long-term stability for oxygen evolution reaction (OER) are essential for electrocatalytic water splitting. Ni foam (NF) is highlighted for its 3D porous structure, impressive conductivity and large specific surface area. Herein, nano/micro structured dendritic cobalt activated nickel sulfide grown on 3D porous NF (Co–Ni3S2/NF) has been successfully synthesized by one-step hydrothermal method. Due to the ingenious incorporation of Co, Co–Ni3S2/NF electrode shows auspicious electrocatalytic performance for OER compared with Ni3S2/NF electrode. As a result, Co–Ni3S2/NF needs overpotential of only 274 and 459 mV at current density of 10 and 50 mA cm−2, respectively, while Ni3S2/NF requires overpotential of 344 and 511 mV. At potential of 2.0 V (vs. RHE), Co–Ni3S2/NF displays current density of 191 mA cm−2, while Ni3S2/NF just attains current density of only 135 mA cm−2. Moreover, Co–Ni3S2/NF demonstrates excellent stability for uninterrupted OER in alkaline electrolyte. The strategy of designing and preparing cobalt activated nickel sulfide grown on NF renders a magnificent prospect for the development of metal-sulfide-based oxygen evolution catalysts with excellent electrocatalytic performances.  相似文献   

9.
The synthesis of cost-effective and high-performance electrocatalysts for water splitting is the main challenge in electrochemical hydrogen production. In this study, we adopted a high throughput method to prepare bi-metallic catalysts for oxygen/hydrogen evolution reactions (OER/HER). A series of Ni–Mo alloy electrocatalysts with tunable compositions were prepared by a simple co-sputtering method. Due to the synergistic effect between Ni and Mo, the intrinsic electrocatalytic activity of the Ni–Mo alloy electrocatalysts is improved, resulting in excellent HER and OER performances. The Ni90Mo10 electrocatalyst shows the best HER performance, with an extremely low overpotential of 58 mV at 10 mA cm?2, while the Ni40Mo60 electrocatalyst shows an overpotential of 258 mV at 10 mA cm?2 in OER. More significantly, the assembled Ni40Mo60//Ni90Mo10 electrolyzer only needs a cell voltage of 1.57 V to reach 10 mA cm?2 for overall water splitting.  相似文献   

10.
The construction of cost-effective bifunctional electrocatalysts with the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) is significant for efficient overall water splitting. Herein, this work demonstrates a novel strategy for the synthesis of nickel-cobalt oxides/sulfides/phosphides composite (denoted as NiCoO–2P/S) nanoarrays on Ni foam. In this method, Ni–Co bimetallic oxide nanowires on Ni foam were partially phosphorized and sulfurized simultaneously in situ to yield Ni–Co oxide/sulfide/phosphide composite. The NiCoO–2P/S arrays have good interfacial effects and display many holes in the nanowires, giving it the advantage of large accessible surfaces on the nanowires and a beneficial for the release of gas bubbles, resulting in an excellent OER performance with a low overpotential (η) of 254 mV at 100 mA cm?2 and good HER activity (η10 = 143 mV at 10 mA cm?2). The electrocatalytic test results demonstrate small Tafel slopes (82 mV dec?1 for HER, 88 mV dec?1 for OER) and the satisfying durability in an alkaline electrolyte, indicating that the HER and OER activity was enhanced by the introduction of the Ni/Co sulfides and phosphides into Ni–Co oxides composite nanowires. Furthermore, the as-prepared NiCoO–2P/S catalyst can be used as both the anode and the cathode simultaneously to realize overall water splitting in the two-electrode electrolyzer. This system can be driven at low cell voltages of 1.50 and 1.68 V to achieve current densities of 10 and 100 mA cm?2, respectively. This work provides an alternative strategy to prepare high-performance bifunctional electrochemical materials and demonstrates the advantages of Ni–Co oxide/sulfide/phosphide composites for water splitting.  相似文献   

11.
The exploration of electrocatalysts with high oxygen evolution reaction (OER) activity is highly desirable and remains a significant challenge. Transition metal carbides (TMCs) have been investigated as remarkable hydrogen evolution reaction (HER) electrocatalysts but few used as oxygen evolution reaction (OER) electrocatalysts. Herein, a Co doped Ni3C/Ni uniformly dispersed in a graphitic carbon matrix was prepared by pyrolysis of a metal organic framework (Co/Ni-MOF) under a flow of Ar/H2 at 350 °C, and Ni3C/Ni@C was also prepared for comparison. The various characterization techniques confirmed the successful preparation of the heteroatom doped TMCs-based catalysts by pyrolysis of MOFs. Co doped Ni3C/Ni@C exhibited superior electrocatalytic properties for OER. For example, Co–Ni3C/Ni@C depicts a lower overpotential and smaller Tafel slope than Ni3C/Ni@C and IrO2 during the OER in 1 M KOH solution, additionally, it shows a higher active surface area than Ni3C/Ni@C. The outstanding electrocatalytic performance of Co-doped Ni3C/Ni@C in the OER was mainly ascribed to the synergistic effect of the Co and Ni3C/Ni active sites.  相似文献   

12.
Electrocatalytic water splitting is an emerging technology for the development of maintainable hydrogen energy. It remains challenging to manufacture a stable, efficient, and cost-effective electrocatalyst that can conquer the slow reaction kinetics of water electrolysis. Herein, A metal-organic framework (MOF) based material is manufactured and productively catalyze the oxygen evolution reaction (OER). The introduction of elemental nickel enhances the catalytic activity of Co-FcDA. The results show that single Ni was well doped in the CoNi-FcDA catalysts and the doping of Ni has a great influence on the OER activity of CoNi-FcDA catalysts. CoNi-FcDA displayed a low overpotential of 241 mV to arrive at the benchmark current density (10 mA cm?2) with a remarkably small Tafel slope of 78.63 mV dec?1. It surpassed the state-of-the-art electrocatalyst for OER, that is, RuO2 (260 mV and 97.26 mV dec?1) in efficiency as well as instability. Density functional theory (DFT) calculations show that suitable Ni doping at the same time can increase the density of states of the Fermi level, resulting in excellent charge density and low intermediate adsorption energy. These discoveries provide a practical route for designing 2D polymetallic nanosheets to optimize catalytic OER performance.  相似文献   

13.
Developing non-noble metal catalysts with excellent electrocatalytic performance and stability is of great significance to hydrogen production by water electrolysis, but there are still problems of low activity, complex preparation and high cost. Herein, we fabricated a novel Ni3S2/Ni(OH)2 dual-functional electrocatalyst by a one-step fast electrodeposition on nickel foam (NF). While maintaining the electrocatalytic performance of Ni3S2, the existence of heterostructure and Ni(OH)2 co-catalyst function greatly improves the overall water splitting performance of Ni3S2/Ni(OH)2–NF. Hence, It shows a low overpotential of 66 mV at 10 mA cm?2 for HER and 249 mV at 20 mA cm?2 for OER. The dual-functional electrocatalyst needs only 1.58 V at 20 mA cm?2 when assembled two-electrode electrolytic cell. Impressively, the electrocatalyst also shows outstanding catalytic stability for about 800 h when 20 and 50 mA cm?2 constant current was applied, respectively which demonstrates a potential electrocatalyst for overall water splitting.  相似文献   

14.
Multi-shelled NiO/Ni/Graphene and Co3O4/Co/Graphene nano-spheres for high performance electrocatalytic activity in water electrolysis have been synthesized using multi-step solvothermal process. The synthesis process was derived by Metal-Organic-Framework (MOF) with the successive carbonization and oxidation treatments, which results into the formation of NiO/Ni and Co3O4/Co nano-crystalline particles with a coverage of graphene shell. In the present work, the effect of variation in concentration of polyvinyl pyrrole (PVP) during synthesis has also been executed. XRD studies were confirmed the formation of Co0 and Co3O4 in Co3O4/Co/Graphene sample and Ni0 and NiO in NiO/Ni/Graphene. In both cases, the surface area values showed inclining nature with increase in the amount of PVP, till 1.21 g and 1.31 g during their synthesis for nickel and cobalt, respectively. Moreover, the nano-materials could not sustain their spherical shape above the optimal concentration of PVP during synthesis. The optimal concentration of PVP has been determined as 1.21 and 1.31 g in the nickel and cobalt nano-sphere formation, respectively. The SEM and TEM images have affirmed the morphological transformations from the MOFs to MxOy/M/graphene structures. The average diameter of MOFs got shrank down from 60 – 70 nm to 20–30 nm in MxOy/M/graphene nanospheres. It get decreased above the optimum concentration of PVP. The highest surface area value reached to 151.3 m2/g in the Co3O4/Co/graphene prepared with 1.31 g of PVP, whereas same with nickel it touched to maximum value of 146.5 m2/g with PVP concentration of 1.21 g. Both the materials were exhibited excellent electrocatalytic activity in HER and OER during water electrolysis in acidic media, however, Cobalt catalysts performed better in hydrogen production. The anodic and cathodic peak current density has reached maximum value of 50 and 30 A cm?2 in presence of cobalt catalysts (with 1.31 g of PVP). The performance of Co3O4/Co/graphene nano-sphere (1.31 g PVP) is evaluated up to 10 A cm?2, whereas this value is only analyzed as 3 A cm?2 in the case of cobalt non-sphere electrocatalysts during anodic polarization. All the hollow spherical nano-electrocatalysts have shown the electrocatalytic stability during 84 h long potentiometric study.  相似文献   

15.
Highly active and stable non-precious metal dual-functional electrocatalysts for the hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are very important for the industrialization of water electrolysis. Herein, a three-dimensional (3D) porous CoS2/FeS-MOF with adjustable Co/Fe molar ratio are in-stiu grown on a nickel foam (NF) to get a binder-free electrocatalyst electrode for HER and OER (CoS2/FeS-MOF@NF). It should be emphasized that the MOFs precursor forms abundant heterogeneous interfaces through in-situ sulfidation. Moreover, the open skeleton and ordered porous structure of MOFs will not be destroyed due to the low temperature. The redistribution of electrons at the heterogeneous interfaces will produce more catalytic active centers, providing more active sites for reactant molecules or intermediates, thus availably promoting the electrocatalytic activity of the composite. Therefore, the optimized catalyst CoS2/FeS-MOF@NF-1 displays high OER activity. The overpotential is only 136 mV at 10 mA cm?2. At the same time, the CoS2/FeS-MOF@NF-1 also shows good HER catalytic activity. Therefore, the assembled corresponding symmetric electrolyzer CoS2/FeS-MOF@NF-1||CoS2/FeS-MOF@NF-1 achieves a low cell voltage of 1.5 V at 10 mA cm?2 with long time stability for 24 h. This work provides a simple and convenient strategy for the synthesis of transition metal sulfides dual-function electrocatalysts.  相似文献   

16.
The development of highly efficient and low-cost electrocatalysts is critical to the mass production of hydrogen from water splitting. Herein, a facile yet effective method was developed to synthesize bimetallic sulfides Ni3S2/CoSx, which were aimed for use as the electrocatalysts in both HER and OER. Encouragingly, the Ni3S2/CoSx demonstrated a low overpotential of 110 mV for HER at a current density of 10 mA·cm?2. It was discovered that the surface of Ni3S2/CoSx during OER process would undergo an in-situ oxidation to form MOOH (M = Co, Ni), that is, MOOH/Ni3S2/CoSx were the real functioning species in catalysis, which had an excellent OER activity and a low overpotential of 226 mV. Additionally, the assembled electrolyzer required only a low cell voltage of 1.53 V to achieve a current density of 10 mA·cm?2 in a 1 M KOH solution, and its performance was stable. Overall, this work provided a promising strategy for the facile fabrication of low-cost amorphous electrocatalysts, which is expected to promote the progress of overall water splitting.  相似文献   

17.
To alleviate the sluggish oxygen evolution reaction (OER) kinetics, it's urgent to develop electrocatalysts with high activity and low cost. In this work, Fe doped metal organic frameworks (Ni)/carbon black composites were synthesized via a facile hydrothermal method. Benefiting from the direct use of metal organic frameworks (MOFs) for OER, numerous and highly dispersed active sites are exposed to the electrolyte and reactants. By regulating Ni/Fe ratios, a high electrochemical active surface area (ECSA) and high relative surface content of active Ni3+ species are obtained, which mainly contribute to the high OER activity. Besides, the introduced carbon black (CB) was found to enhance the charge-transfer efficiency of the electrocatalysts, which is also favorable for OER. The optimal Ni9Fe1-BDC-0.15CB electrocatalyst shows excellent OER activity with the low overpotential of ~290 mV at 10 mA cm−2 and the Tafel slope of ~76.1 mV dec−1, which is comparable to RuO2 and other MOFs-based OER electrocatalysts reported in recent years.  相似文献   

18.
Constructing highly efficient nonprecious electrocatalysts for oxygen evolution reaction (OER) and hydrogen evolution reaction (HER) is essential to improve the efficiency of overall water splitting, but still remains lots of obstacles. Herein, a novel 3D peony flower-like electrocatalyst was synthesized by employing Mo–Ni2S3/NF nanorod arrays as scaffolds to in situ growth ultrathin NiFe LDH nanosheets (Mo-Ni2S3@NiFe LDH). As expected, the novel peony flower-like Mo–Ni2S3@NiFe LDH displays superior electrocatalytic activity and stability for both OER and HER in alkaline media. Low overpotentials of only 228 mV and 109 mV are required to achieve the current densities of 50 mA cm?2 and 10 mA cm?2 for OER and HER, respectively. Additionally, the material remarkably accelerates water splitting with a low voltage of 1.54 V at 10 mA cm?2, which outperforms most transition metal electrodes. The outstanding electrocatalytic activity benefits from the following these features: 3D peony flower-like structure with rough surface provides more accessible active sites; superhydrophilic surfaces lead to the tight affinity between electrode with electrolyte; metallic Ni substrate and highly conductive Mo–Ni2S3 nanorods scaffold together with offer fast electron transfer; the nanorod arrays and porous Ni foam accelerate gas bubble release and ions transmission; the strong interfacial effect between Mo-doped Ni3S2 and NiFe LDH shortens transport pathway, which are benefit for electrocatalytic performance enhancement. This work paves a new avenue for construction and fabrication the 3D porous structure to boost the intrinsic catalytic activities for energy conversion and storage applications.  相似文献   

19.
The design of multi-components nanostructure with interface heterojunction is the cutting-edge research in recent years because the catalytic activity, stability, and durability of catalysts are highly affected by the strong electronic effects, geometric effects, and synergistic effects occurring at the interface. Based on this, an efficient bifunctional electrocatalyst embedding highly dispersed Ni2P/Co nano heterojunction at the porous hollow-out carbon shell is developed for overall water splitting through evenly epitaxial growth of ultrathin Ni2P nanosheets on Co-based ZIF-67. The distinct electron interaction between the interfacial Ni2P (300) and Co (100) effectively lowers the overpotential of OER (316 mV vs. RHE) and HER (149 mV vs. RHE) at the current density of 10 mA cm?2. Density functional theory (DFT) calculation further identifies that the Ni2P and Co heterojunctions optimize the adsorption energy of intermediate products and lower the energy barrier of the rate-determining step of OER significantly. This work provides a rational design of a well-defined interface toward overall water splitting electrocatalysts and offers a scientific basis for an in-depth understanding of the mechanism of the catalysts with nano heterojunction.  相似文献   

20.
Searching for high-performance and earth-abundant electrocatalysts for oxygen evolution reaction (OER) is of paramount significance for overall water splitting to produce hydrogen. Herein, an advanced class of CoNi selenides containing rich oxygen vacancies, with a hierarchical bundle-like and holey nanosheets as noble-metal-free catalysts were first synthesized through a facile hydrothermal method. Benefitting from abundant oxygen vacancies, bundle-like nanostructure, as well as strong synergistic effects, such CoNi selenides demonstrate a greatly enhanced surface area to supply more electrocatalytic active sites to contact with electrolyte, accompanied by largely promoted reaction kinetics, which show outstanding electrocatalytic performances for OER. Remarkably, the optimal Co1Ni0.5Se can display outstanding OER activity with the small Tafel slope of 48 mV dec−1 and low overpotential of 250 mV (at 10 mA cm−2), which are much superior to those of Co/Ni-based catalysts. This electrocatalyst can also maintain high activity and structure stability during long-term electrolysis of 35 h, demonstrating a desirable electrocatalyst for OER. This work elucidates the sophisticated construction of well-defined non-noble metal catalysts for the practical applications in water oxidation.  相似文献   

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