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1.
Photosynthesis in nature uses the Mn4CaO5 cluster as the oxygen-evolving center to catalyze the water oxidation efficiently in photosystem II. Herein, we demonstrate bio-inspired heterometallic LnCo3 (Ln = Nd, Eu and Ce) clusters, which can be viewed as synthetic analogs of the CaMn4O5 cluster. Anchoring LnCo3 on phosphorus-doped graphitic carbon nitrides (PCN) shows efficient overall water splitting without any sacrificial reagents. The NdCo3/PCN-c photocatalyst exhibits excellent water splitting activity and a quantum efficiency of 2.0% at 350 nm. Ultrafast transient absorption spectroscopy revealed the transfer of a photoexcited electron and hole into the PCN and LnCo3 for hydrogen and oxygen evolution reactions, respectively. A density functional theory (DFT) calculation showed the cooperative water activation on lanthanide and O−O bond formation on transition metal for water oxidation. This work not only prepares a synthetic model of a bio-inspired oxygen-evolving center but also provides an effective strategy to realize light-driven overall water splitting.  相似文献   

2.
Most metal–organic frameworks (MOFs) hardly maintain their physical and chemical properties after exposure to alkaline aqueous solutions, thus precluding their use as potential electrode materials for electrochemical energy storage devices. Here, we present the design and synthesis of a highly alkaline-stable metal oxide@MOF composite, Co3O4 nanocube@Co-MOF (Co3O4@Co-MOF), via a controllable and facile one-pot hydrothermal method under highly alkaline conditions. The obtained composite possesses exceptional alkaline stability, retaining its original structure in 3.0 M KOH for at least 15 days. Benefitting from the exceptional alkaline stability, unique structure, and larger surface area, the Co3O4@Co-MOF composite shows a specific capacitance as high as 1020 F g−1 at 0.5 A  g−1 and a high cycling stability with only 3.3% decay after 5000 cycles at 5 A g−1. The as-constructed solid-state flexible device exhibits a maximum energy density of 21.6 mWh cm−3.  相似文献   

3.
Activation of high-energy triple-bonds of N2 is the most significant bottleneck of ammonia synthesis under ambient conditions. Here, by importing cobalt single clusters as strong electron-donating promoter into the catalyst, the rate-determining step of ammonia synthesis is altered to the subsequent proton addition so that the barrier of N2 dissociation can be successfully overcome. As revealed by density functional theory calculations, the N2 dissociation becomes exothermic over the cobalt single cluster upon the strong electron backdonation from metal to the N2 antibonding orbitals. The energy barrier of the positively shifted rate-determining step is also greatly reduced. At the same time, advanced sampling molecular dynamics simulations indicate a barrier-less process of the N2 approaching the active sites that greatly facilitates the mass transfer. With suitable thermodynamic and dynamic property, a high ammonia yield rate of 76.2 μg h–1 mg and superior Faradaic efficiency of 52.9% were simultaneously achieved.  相似文献   

4.
中药产业集群类型及进化路径分析   总被引：1，自引：0，他引：1  
以产业层次、结构形式二维刻画中药产业集群类型,并以矩阵联系类分9种中药产业集群,以结构进化为中轴分析它们的进化路径和进化规律。  相似文献   

5.
Understanding the mineralogy of the Earth''s interior is a prerequisite for unravelling the evolution and dynamics of our planet. Here, we conducted high pressure-temperature experiments mimicking the conditions of the deep lower mantle (DLM, 1800–2890 km in depth) and observed surprising mineralogical transformations in the presence of water. Ferropericlase, (Mg, Fe)O, which is the most abundant oxide mineral in Earth, reacts with H2O to form a previously unknown (Mg, Fe)O2Hx (x ≤ 1) phase. The (Mg, Fe)O2Hx has a pyrite structure and it coexists with the dominant silicate phases, bridgmanite and post-perovskite. Depending on Mg content and geotherm temperatures, the transformation may occur at 1800 km for (Mg0.6Fe0.4)O or beyond 2300 km for (Mg0.7Fe0.3)O. The (Mg, Fe)O2Hx is an oxygen excess phase that stores an excessive amount of oxygen beyond the charge balance of maximum cation valences (Mg2+, Fe3+ and H+). This important phase has a number of far-reaching implications including extreme redox inhomogeneity, deep-oxygen reservoirs in the DLM and an internal source for modulating oxygen in the atmosphere.  相似文献   

6.
Although β-Fe2O3 has a high theoretical solar-to-hydrogen efficiency because of its narrow band gap, the study of β-Fe2O3 photoanodes for water splitting is elusive as a result of their metastable nature. Raman identification of β-Fe2O3 is theoretically and experimentally investigated in this study for the first time, thus clarifying the debate about its Raman spectrum in the literature. Phase transformation of β-Fe2O3 to α-Fe2O3 was found to potentially take place under laser and electron irradiation as well as annealing. Herein, phase transformation of β-Fe2O3 to α-Fe2O3 was inhibited by introduction of Zr doping, and β-Fe2O3 was found to withstand a higher annealing temperature without any phase transformation. The solar water splitting photocurrent of the Zr-doped β-Fe2O3 photoanode was increased by 500% compared to that of the pure β-Fe2O3 photoanode. Additionally, Zr-doped β-Fe2O3 exhibited very good stability during the process of solar water splitting. These results indicate that by improving its thermal stability, metastable β-Fe2O3 film is a promising photoanode for solar water splitting.  相似文献   

7.
集群知识网络的内生演化研究——基于多主体的仿真分析   总被引：1，自引：0，他引：1  
陈金丹  胡汉辉  吉敏 《情报杂志》2012,31(7):128-133
理解集群知识网络的内生演化机理与过程对于提升集群竞争力有着重要的现实意义.从集群知识网络中网络关系出发,按照从微观到宏观的思维逻辑,剖析了集群知识网络在网络关系和整体网络两个层面上的内生演化机理.将多主体仿真分析与实证研究相结合,模拟了集群知识网络的内生演化过程,并分析其演化结果.研究表明,网络节点基于自身需求对网络关系的选择行为遗传或变异着网络结构,导致了集群知识网络的涌现;经过一段时间的演化后,集群知识网络规模趋于稳定,具有较为明显的小世界网络特征和倾斜的度分布曲线.  相似文献   

8.
Sodium-based dual-ion batteries (Na-DIBs) show a promising potential for large-scale energy storage applications due to the merits of environmental friendliness and low cost. However, Na-DIBs are generally subject to poor rate capability and cycling stability for the lack of suitable anodes to accommodate large Na+ ions. Herein, we propose a molecular grafting strategy to in situ synthesize tin pyrophosphate nanodots implanted in N-doped carbon matrix (SnP2O7@N-C), which exhibits a high fraction of active SnP2O7 up to 95.6 wt% and a low content of N-doped carbon (4.4 wt%) as the conductive framework. As a result, this anode delivers a high specific capacity ∼400 mAh g−1 at 0.1 A g−1, excellent rate capability up to 5.0 A g−1 and excellent cycling stability with a capacity retention of 92% after 1200 cycles under a current density of 1.5 A g−1. Further, pairing this anode with an environmentally friendly KS6 graphite cathode yields a SnP2O7@N-C||KS6 Na-DIB, exhibiting an excellent rate capability up to 30 C, good fast-charge/slow-discharge performance and long-term cycling life with a capacity retention of ∼96% after 1000 cycles at 20 C. This study provides a feasible strategy to develop high-performance anodes with high-fraction active materials for Na-based energy storage applications.  相似文献   

9.
Herein, a wide-spectrum (∼678 nm) responsive Bi8(CrO4)O11 photocatalyst with a theoretical solar spectrum efficiency of 42.0% was successfully constructed. Bi8(CrO4)O11 showed highly efficient and stable photocatalytic water oxidation activity with a notable apparent quantum efficiency of 2.87% (420 nm), superior to many reported wide-spectrum driven photocatalysts. Most remarkably, its strong oxidation ability also enables the simultaneous degradation and complete mineralization for phenol, and its excellent performance is about 23.0 and 2.9 times higher than CdS and P25-TiO2, respectively. Its high activity is ascribed to the giant internal electric field induced by its large crystal dipole, which accelerates the rapid separation of photogenerated electron–hole pairs. Briefly, the discovery of wide-spectrum bismuth chromate and the mechanism of exponentially enhanced photocatalytic performance by increasing the crystal dipole throw light on improving solar energy conversion.  相似文献   

10.
Applying metal organic frameworks (MOFs) in electrochemical systems is a currently emerging field owing to the rich metal nodes and highly specific surface area of MOFs. However, the problems for MOFs that need to be solved urgently are poor electrical conductivity and low ion transport. Here we present a facile in situ growth method for the rational synthesis of MOFs@hollow mesoporous carbon spheres (HMCS) yolk–shell-structured hybrid material for the first time. The size of the encapsulated Zeolitic Imidazolate Framework-67 (ZIF-67) is well controlled to 100 nm due to the spatial confinement effect of HMCS, and the electrical conductivity of ZIF-67 is also increased significantly. The ZIF@HMCS-25% hybrid material obtained exhibits a highly efficient oxygen reduction reaction activity with 0.823 V (vs. reversible hydrogen electrode) half-wave potential and an even higher kinetic current density (JK = 13.8 mA cm−2) than commercial Pt/C. ZIF@HMCS-25% also displays excellent oxygen evolution reaction performance and the overpotential of ZIF@HMCS-25% at 10 mA cm−2 is 407 mV. In addition, ZIF@HMCS-25% is further employed as an air electrode for a rechargeable Zn–air battery, exhibiting a high power density (120.2 mW cm−2 at 171.4 mA cm−2) and long-term charge/discharge stability (80 h at 5 mA cm−2). This MOFs@HMCS yolk–shell design provides a versatile method for the application of MOFs as electrocatalysts directly.  相似文献   

11.
产业集群形态演化阶段探讨   总被引：19，自引：0，他引：19  
国内外学者对产业集群的研究大多基于产业集群显现阶段的特征、机制与绩效表现等方面,众多学者对产业集群形态界定的多样性正是产业集群持续演化不同阶段的"快照"。本文根据复杂系统演化的分析思路,提出了产业集群演化的阶段分析模型,揭示了产业集群演化的四个阶段形态,并指出集群政策的核心在于促使产业集群自组织向更高级的阶段形态进化。  相似文献   

12.
Photocatalytic CO2 reduction into energy carriers is of utmost importance due to the rising concentrations of CO2 and the depleting energy resource. However, the highly selective generation of desirable hydrocarbon fuel, such as methane (CH4), from CO2 remains extremely challenging. Herein, we present two stable polyoxometalate-grafted metalloporphyrin coordination frameworks (POMCFs), which are constructed with reductive Zn-ϵ-Keggin clusters and photosensitive tetrakis(4-carboxylphenyl)porphyrin (H2TCPP) linkers, exhibiting high selectivity (>96%) for CH4 formation in a photocatalytic CO2-reduction system. To our knowledge, the high CH4 selectivity of POMCFs has surpassed all of the reported coordination-framework-based heterogeneous photocatalysts for CO2-to-CH4 conversion. Significantly, the introduction of a Zn-ϵ-keggin cluster with strong reducing ability is the important origin for POMCFs to obtain high photocatalytic selectivity for CH4 formation, considering that eight MoV atoms can theoretically donate eight electrons to fulfill the multielectron reduction process of CO2-to-CH4 transformation.  相似文献   

13.
Marine diatoms construct their hierarchically ordered, three-dimensional (3D) external structures called frustules through precise biomineralization processes. Recapitulating the remarkable architectures and functions of diatom frustules in artificial materials is a major challenge that has important technological implications for hierarchically ordered composites. Here, we report the construction of highly ordered, mineralized composites based on fabrication of complex self-supporting porous structures—made of genetically engineered amyloid fusion proteins and the natural polysaccharide chitin—and performing in situ multiscale protein-mediated mineralization with diverse inorganic materials, including SiO2, TiO2 and Ga2O3. Subsequently, using sugar cubes as templates, we demonstrate that 3D fabricated porous structures can become colonized by engineered bacteria and can be functionalized with highly photoreactive minerals, thereby enabling co-localization of the photocatalytic units with a bacteria-based hydrogenase reaction for a successful semi-solid artificial photosynthesis system for hydrogen evolution. Our study thus highlights the power of coupling genetically engineered proteins and polysaccharides with biofabrication techniques to generate hierarchically organized mineralized porous structures inspired by nature.  相似文献   

14.
首先分析区域装备制造业集群形成的原因,在此基础上对区域装备制造业集群演化的过程与特征进行分析,从而探求区域装备制造业集群演化的机理,最后构建出区域装备制造业集群演化的动力机制,本研究对揭示区域装备制造业集群演化的机理具有一定的理论和实践意义。  相似文献   

15.
As a promising low-cost energy storage device, the development of a rechargeable potassium-ion battery (KIB) is severely hindered by the limited capacity of cathode candidates. Regarded as an attractive capacity-boosting strategy, triggering the O-related anionic redox activity has not been achieved within a sealed KIB system. Herein, in contrast to the typical gaseous open K-O2 battery (O2/KO2 redox), we originally realize the reversible superoxide/peroxide (KO2/K2O2) interconversion on a KO2-based cathode. Controlled within a sealed cell environment, the irreversible O2 evolution and electrolyte decomposition (induced by superoxide anion (O2−) formation) are effectively restrained. Rationally controlling the reversible depth-of-charge at 300 mAh/g (based on the mass of KO2), no obvious cell degradation can be observed during 900 cycles. Moreover, benefitting from electrolyte modification, the KO2-based cathode is coupled with a limited amount of K-metal anode (merely 2.5 times excess), harvesting a K-metal full-cell with high energy efficiency (∼90%) and long-term cycling stability (over 300 cycles).  相似文献   

16.
The two-electron reduction of molecular oxygen represents an effective strategy to enable the green, mild and on-demand synthesis of hydrogen peroxide. Its practical viability, however, hinges on the development of advanced electrocatalysts, preferably composed of non-precious elements, to selectively expedite this reaction, particularly in acidic medium. Our study here introduces 2H-MoTe2 for the first time as the efficient non-precious-metal-based electrocatalyst for the electrochemical production of hydrogen peroxide in acids. We show that exfoliated 2H-MoTe2 nanoflakes have high activity (onset overpotential ∼140 mV and large mass activity of 27 A g−1 at 0.4 V versus reversible hydrogen electrode), great selectivity (H2O2 percentage up to 93%) and decent stability in 0.5 M H2SO4. Theoretical simulations evidence that the high activity and selectivity of 2H-MoTe2 arise from the proper binding energies of HOO* and O* at its zigzag edges that jointly favor the two-electron reduction instead of the four-electron reduction of molecular oxygen.  相似文献   

17.
在生态学Lotka-Volterra理论和产业集群生态位整合的Logistic模型基础上建立产业集群生态网络竞合模型。结合产业集群的竞合特征,通过调节竞合系数来讨论企业间的竞合模式,并针对企业不同生态位的表现提出"生态位确立——生态位拓展——生态位巩固——生态位整合——生态位分离"的产业集群生态网络应对战略。最后对产业集群生态网络在竞争和合作的过程中提出注意点,使得生态网络生态位保持稳定。  相似文献   

18.
运用生命周期理论,较为详细地分析了文化创意产业集群演化的各阶段特征,同时为了揭示企业间在集群生命周期各阶段竞争与合作的稳定性,运用Kolmogorov种群相互作用模型分析稳定共生的条件,并在此基础上得出促进集群各阶段稳定发展的对策建议。  相似文献   

19.
《Journal of The Franklin Institute》2019,356(18):11561-11580
This paper addresses the robust H∞ filter design problem for a class of uncertain fuzzy neutral stochastic system with time-delay through Takagi–Sugeno (T–S) fuzzy model. By constructing an augmented Lyapunov–Krasovskii functional, some novel delay-dependent stability criteria for uncertain fuzzy neutral stochastic system with time varying delay are obtained in terms of linear matrix inequalities. By using the integral inequality in the neutral stochastic setting combined with delay decomposition approach, the H∞ fuzzy filter is designed to guarantee the corresponding filtering error systems robustly asymptotically stable with a specified H∞ performance index. At last, two numerical examples are presented to show the less conservatism than the previous results.  相似文献   

20.
经过几十年的演化,产业集群理论已被广泛接受,而产业集群化发展也成为推动区域经济发展的重要途径。我国西部地区现有集群多为基于低成本的传统型产业集群,它们自身的发展出现了很多问题,并且不能持续的推动区域经济,所以着手于创新性产业集群的构建和发展成为当务之急。而基于我国西部具体现状,创新性产业集群的培育和构建应主要依托社会资本和经济资本的充分利用,其升级则要依靠构建国家价值链来实现。  相似文献   

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