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1.
J Am Chem Soc ; 2020 Sep 23.
Artigo em Inglês | MEDLINE | ID: mdl-32924478

RESUMO

Encapsulation of metal nanocatalysts by support-derived materials is well known as a classical strong metal-support interaction (SMSI) effect that occurs almost exclusively with active oxide supports and often blocks metal-catalyzed surface reactions. In the present work this classical SMSI process has been surprisingly observed between metal nanoparticles, e.g., Ni, Fe, Co, and Ru, and inert hexagonal boron nitride (h-BN) nanosheets. We find that weak oxidizing gases such as CO2 and H2O induce the encapsulation of nickel (Ni) nanoparticles by ultrathin boron oxide (BOx) overlayers derived from the h-BN support (Ni@BOx/h-BN) during the dry reforming of methane (DRM) reaction. In-situ surface characterization and theory calculations reveal that surface B-O and B-OH sites in the formed BOx encapsulation overlayers work synergistically with surface Ni sites to promote the DRM process rather than blocking the surface reactions.

2.
Artigo em Inglês | MEDLINE | ID: mdl-32886835

RESUMO

Developing copper-free catalysts for CO2 conversion into hydrocarbons and oxygenates is highly desirable for electrochemical CO2 reduction reaction (CO2 RR). Herein, we report a cobalt phthalocyanine (CoPc) and zinc-nitrogen-carbon (Zn-N-C) tandem catalyst for CO2 RR to CH4 . This tandem catalyst shows a more than 100 times enhancement of the CH4 /CO production rate ratio compared with CoPc or Zn-N-C alone. Density functional theory (DFT) calculations and electrochemical CO reduction reaction results suggest that CO2 is first reduced into CO over CoPc and then CO diffuses onto Zn-N-C for further conversion into CH4 over Zn-N4 site, decoupling complicated CO2 RR pathway on single active site into a two-step tandem reaction. Moreover, mechanistic analysis indicates that CoPc not only generates CO but also enhances the availability of *H over adjacent N sites in Zn-N4 , which is the key to achieve the high CH4 production rate and understand the intriguing electrocatalytic behavior which is distinctive to copper-based tandem catalysts.

3.
Artigo em Inglês | MEDLINE | ID: mdl-32473050

RESUMO

Encapsulating transition-metal nanoparticles inside carbon nanotubes (CNTs) or spheres has emerged as a novel strategy for designing highly durable nonprecious-metal catalysts. The stable carbon layer protects the inner metal core from the destructive reaction environment and thus is described as chain mail for catalysts. Electron transfer from the active metal core to the carbon layer stimulates unique catalytic activity on the carbon surface, which has been utilized extensively in a variety of catalytic reaction systems. Here, we elaborate the underlying working principle of chain mail for catalysts as well as the key factors that determine their catalytic properties, and provide insights into the physicochemical nature of such catalyst architectures for further application of the strategy in rational catalyst design.

4.
Artigo em Inglês | MEDLINE | ID: mdl-32452143

RESUMO

In situ exsolution of metal nanoparticles in perovskite under reducing atmosphere is employed to generate a highly active metal-oxide interface for CO2 electrolysis in a solid oxide electrolysis cell. Atomic-scale insight is provided into the exsolution of CoFe alloy nanoparticles in La0.4 Sr0.6 Co0.2 Fe0.7 Mo0.1 O3-δ (LSCFM) by in situ scanning transmission electron microscopy (STEM) with energy-dispersive X-ray spectroscopy and DFT calculations. The doped Mo atoms occupy B sites of LSCFM, which increases the segregation energy of Co and Fe ions at B sites and improves the structural stability of LSCFM under a reducing atmosphere. In situ STEM measurements visualized sequential exsolution of Co and Fe ions, formation of CoFe alloy nanoparticles, and reversible exsolution and dissolution of CoFe alloy nanoparticles in LSCFM. The metal-oxide interface improves CO2 adsorption and activation, showing a higher CO2 electrolysis performance than the LSCFM counterparts.

5.
ChemSusChem ; 2020 May 27.
Artigo em Inglês | MEDLINE | ID: mdl-32459062

RESUMO

CO2 electroreduction by solid oxide electrolysis cells (SOECs) can not only attenuate the greenhouse effect, but also convert surplus electrical energy into chemical energy. The adsorption and activation of CO2 on the cathode play an important role in the SOEC performance. La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ -Ce0.8 Sm0.2 O2-δ (LSCF-SDC; SDC=samarium-doped ceria) is a promising SOEC cathode. However, its electrocatalytic activity still needs to be improved. In this study, Pt/SDC interfaces are constructed by decorating Pt nanoparticles onto the SDC surface. Electrochemical measurements indicate that the polarization resistance of the SOEC is decreased from 0.308 to 0.120â€…Ω cm2 , and the current density is improved from 0.913 to 1.420 A cm-2 at 1.6 V and 800 °C. Physicochemical characterizations suggest that construction of the Pt/SDC interfaces increases the oxygen vacancy concentration on the cathode and boosts CO2 adsorption and dissociation, which leads to enhanced CO2 electroreduction performance in SOECs.

6.
Nat Commun ; 11(1): 2312, 2020 May 08.
Artigo em Inglês | MEDLINE | ID: mdl-32385230

RESUMO

Despite tremendous importance in catalysis, the design of oxide-metal interface has been hampered by the limited understanding of the nature of interfacial sites and the oxide-metal interaction (OMI). Through construction of well-defined Cu2O/Pt, Cu2O/Ag and Cu2O/Au interfaces, we find that Cu2O nanostructures (NSs) on Pt exhibit much lower thermal stability than on Ag and Au, although they show the same structure. The activities of these interfaces are compared for CO oxidation and follow the order of Cu2O/Pt > Cu2O/Au > Cu2O/Ag. OMI is found to determine the activity and stability of supported Cu2O NSs, which could be described by the formation energy of interfacial oxygen vacancy. Further, electronic interaction between Cu+ and metal substrates is found center to OMI, where the d band center could be used as a key descriptor. Our study provides insight for OMI and for the development of Cu-based catalysts for low temperature oxidation reactions.

7.
Artigo em Inglês | MEDLINE | ID: mdl-32227428

RESUMO

Perturbing the electronic structure of the MoS2 basal plane by confining heteroatoms offers the opportunity to trigger in-plane activity for the hydrogen evolution reaction (HER). The key challenge consists of inducing the optimum HER activity by controlling the type and distribution of confined atoms. A distance synergy of MoS2 -confined single-atom rhodium is presented, leading to an ultra-high HER activity at the in-plane S sites adjacent to the rhodium. By optimizing the distance between the confined Rh atoms, an ultra-low overpotential of 67 mV is achieved at a current density of 10 mA cm-2 in acidic solution. Experiments and first-principles calculations demonstrate a unique distance synergy between the confined rhodium atoms in tuning the reactivity of neighboring in-plane S atoms, which presents a volcanic trend with the inter-rhodium distance. This study provides a new strategy to tailor the activity of MoS2 surface via modulating the distance between confined single atoms.

8.
ACS Nano ; 2020 Feb 12.
Artigo em Inglês | MEDLINE | ID: mdl-32031780

RESUMO

Wafer-scale monocrystalline two-dimensional (2D) materials can theoretically be grown by seamless coalescence of individual domains into a large single crystal. Here we present a concise study of the coalescence behavior of crystalline 2D films using a combination of complementary in situ methods. Direct observation of overlayer growth from the atomic to the millimeter scale and under model- and industrially relevant growth conditions reveals the influence of the film-substrate interaction on the crystallinity of the 2D film. In the case of weakly interacting substrates, the coalescence behavior is dictated by the inherent growth kinetics of the 2D film. It is shown that the merging of coaligned domains leads to a distinct modification of the growth dynamics through the formation of fast-growing high-energy edges. The latter can be traced down to a reduced kink-creation energy at the interface between well-aligned domains. In the case of strongly interacting substrates, the lattice mismatch between film and substrate induces a pronounced moiré corrugation that determines the growth and coalescence behavior. It furthermore imposes additional criteria for seamless coalescence and determines the structure of grain boundaries. The experimental findings, obtained here for the case of graphene, are confirmed by theory-based growth simulations and can be generalized to other 2D materials that show 3- or 6-fold symmetry. Based on the gained understanding of the relation between film-substrate interaction, shape evolution, and coalescence behavior, conditions for seamless coalescence and, thus, for the optimization of large-scale production of monocrystalline 2D materials are established.

9.
Adv Mater ; 32(6): e1906193, 2020 Feb.
Artigo em Inglês | MEDLINE | ID: mdl-31894628

RESUMO

Reversible exsolution and dissolution of metal nanoparticles in perovskite has been investigated as an efficient strategy to improve CO2 electrolysis performance. However, fundamental understanding with regard to the reversible exsolution and dissolution of metal nanoparticles in perovskite is still scarce. Herein, in situ exsolution and dissolution of CoFe alloy nanoparticles in Co-doped Sr2 Fe1.5 Mo0.5 O6-δ (SFMC) revealed by in situ X-ray diffraction, scanning transmission electron microscopy, environmental scanning electron microscopy, and density functional theory calculations are reported. Under a reducing atmosphere, facile exsolution of Co promotes reduction of the Fe cation to generate CoFe alloy nanoparticles in SFMC, accompanied by structure transformation from double perovskite to layered perovskite at 800 °C. Under an oxidizing atmosphere, spherical CoFe alloy nanoparticles are first oxidized to flat CoFeOx nanosheets, and then dissolved into the bulk with structure evolution from layered perovskite back to double perovskite. Electrochemically, CO2 electrolysis performance can be retrieved during 12 redox cycles due to the regenerative ability of the CoFe alloy nanoparticles. The anchoring of the CoFe alloy nanoparticles in SFMC perovskite via reduction shows enhanced CO2 electrolysis performance and stability compared with the parent SFMC perovskite.

10.
Artigo em Inglês | MEDLINE | ID: mdl-31944516

RESUMO

The electrochemical CO2 reduction reaction (CO2 RR) to give C1 (formate and CO) products is one of the most techno-economically achievable strategies for alleviating CO2 emissions. Now, it is demonstrated that the SnOx shell in Sn2.7 Cu catalyst with a hierarchical Sn-Cu core can be reconstructed in situ under cathodic potentials of CO2 RR. The resulting Sn2.7 Cu catalyst achieves a high current density of 406.7±14.4 mA cm-2 with C1 Faradaic efficiency of 98.0±0.9 % at -0.70 V vs. RHE, and remains stable at 243.1±19.2 mA cm-2 with a C1 Faradaic efficiency of 99.0±0.5 % for 40 h at -0.55 V vs. RHE. DFT calculations indicate that the reconstructed Sn/SnOx interface facilitates formic acid production by optimizing binding of the reaction intermediate HCOO* while promotes Faradaic efficiency of C1 products by suppressing the competitive hydrogen evolution reaction, resulting in high Faradaic efficiency, current density, and stability of CO2 RR at low overpotentials.

11.
Artigo em Inglês | MEDLINE | ID: mdl-31960561

RESUMO

Despite significant progress achieved in Fischer-Tropsch synthesis (FTS) technology, control of product selectivity remains a challenge in syngas conversion. Herein, we demonstrate that Zn2+ -ion exchanged ZSM-5 zeolite steers syngas conversion selectively to ethane with its selectivity reaching as high as 86 % among hydrocarbons (excluding CO2 ) at 20 % CO conversion. NMR spectroscopy, X-ray absorption spectroscopy, and X-ray fluorescence indicate that this is likely attributed to the highly dispersed Zn sites grafted on ZSM-5. Quasi-in-situ solid-state NMR, obtained by quenching the reaction in liquid N2 , detects C2 species such as acetyl (-COCH3 ) bonding with an oxygen, ethyl (-CH2 CH3 ) bonding with a Zn site, and epoxyethane molecules adsorbing on a Zn site and a Brønsted acid site of the catalyst, respectively. These species could provide insight into C-C bond formation during ethane formation. Interestingly, this selective reaction pathway toward ethane appears to be general because a series of other Zn2+ -ion exchanged aluminosilicate zeolites with different topologies (for example, SSZ-13, MCM-22, and ZSM-12) all give ethane predominantly. By contrast, a physical mixture of ZnO-ZSM-5 favors formation of hydrocarbons beyond C3+ . These results provide an important guide for tuning the product selectivity in syngas conversion.

12.
Adv Sci (Weinh) ; 6(23): 1902147, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31832329

RESUMO

With the relentless development of smart and miniaturized electronics, the worldwide thirst for microscale electrochemical energy storage devices with form factors is launching a new era of competition. Herein, the first prototype planar sodium-ion microcapacitors (NIMCs) are constructed based on the interdigital microelectrodes of urchin-like sodium titanate as faradaic anode and nanoporous activated graphene as non-faradaic cathode along with high-voltage ionogel electrolyte on a single flexible substrate. By effectively coupling with battery-type anode and capacitor-type cathode, the resultant all-solid-state NIMCs working at 3.5 V exhibit a high volumetric energy density of 37.1 mWh cm-3 and an ultralow self-discharge rate of 44 h from V max to 0.6 V max, both of which surpass most reported hybrid micro-supercapacitors. Through tuning graphene layer covered on the top surface of interdigital microelectrodes, the NIMCs unveil remarkably enhanced power density, owing to the establishment of favorable multidirectional fast ion diffusion pathways that significantly reduce the charge transfer resistance. Meanwhile, the as-fabricated NIMCs present excellent mechanical flexibility without capacitance fade under repeated deformation, and electrochemical stability at a high temperature of 80 °C because of using nonflammable ionogel electrolyte and in-plane geometry. Therefore, these flexible planar NIMCs with multidirectional ion diffusion pathways hold tremendous potential for microelectronics.

14.
J Chem Phys ; 151(21): 214704, 2019 Dec 07.
Artigo em Inglês | MEDLINE | ID: mdl-31822092

RESUMO

Under the oxidizing condition, the cheap metal component of bimetallic catalysts often segregates to the surface and forms oxide nanoclusters (NCs) supported on the metal surface, which exhibit unique structures and catalytic properties drastically different from the corresponding bulk materials. Here, density functional theory calculations are employed to describe the atomic and electronic structures of a series of triangular FeOx NCs confined on Pt(111) with the size ranging from ∼0.3 nm to ∼2.2 nm, which behave differently from the FeO film reported previously. The lattice of supported FeOx NCs on Pt(111) is found to vary not only with the NC size but also with the Fe/O ratio or the edge termination. Owing to a strong FeOx-Pt interaction, the heterogeneous distribution of local atomic and electronic structures of Fe across the FeOx NC is observed, though most of Fe atoms are positioned at the threefold hollow site of Pt(111). Our study not only sheds light on the catalytically active sites of supported FeOx NCs but also provides guidance for the design of highly active and stable oxide nanocatalysts under reactive environment.

15.
J Am Chem Soc ; 141(45): 18318-18324, 2019 Nov 13.
Artigo em Inglês | MEDLINE | ID: mdl-31644275

RESUMO

A large amount of zeolite structures are still not synthetically available or not available in the form of aluminosilicate currently. Despite significant progress in the development of predictive concepts for zeolite synthesis, accessing some of these new materials is still challenging. One example is the IWR structure as well. Despite successful synthesis of Ge-based IWR zeolites, direct synthesis of aluminosilicate IWR zeolite is still not successful. In this report we show how a suitable organic structure directing agent (OSDA), through modeling of an OSDA/zeolite cage interaction, could access directly the aluminum-containing IWR structure (denoted as COE-6), which might allow access to new classes of materials and thus open opportunities in valuable chemical applications. The experimental results reveal that the COE-6 zeolites with a SiO2/Al2O3 ratio as low as 30 could be obtained. Very interestingly, the COE-6 zeolite has much higher hydrothermal and thermal stabilities than those of the conventional Ge-Al-IWR zeolite. In methanol-to-propylene (MTP) reaction, the COE-6 zeolite exhibits excellent selectivity for propylene, offering a potential catalyst for MTP reaction in the future.

16.
Adv Mater ; 31(50): e1902044, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31483546

RESUMO

High-performance uncooled photodetectors operating in the long-wavelength infrared and terahertz regimes are highly demanded in the military and civilian fields. Photothermoelectric (PTE) detectors, which combine photothermal and thermoelectric conversion processes, can realize ultra-broadband photodetection without the requirement of a cooling unit and external bias. In the last few decades, the responsivity and speed of PTE-based photodetectors have made impressive progress with the discovery of novel thermoelectric materials and the development of nanophotonics. In particular, by introducing hot-carrier transport into low-dimensional material-based PTE detectors, the response time has been successfully pushed down to the picosecond level. Furthermore, with the assistance of surface plasmon, antenna, and phonon absorption, the responsivity of PTE detectors can be significantly enhanced. Beyond the photodetection, PTE effect can also be utilized to probe exotic physical phenomena in spintronics and valleytronics. Herein, recent advances in PTE detectors are summarized, and some potential strategies to further improve the performance are proposed.

17.
Adv Mater ; 31(41): e1903470, 2019 Oct.
Artigo em Inglês | MEDLINE | ID: mdl-31441152

RESUMO

Simultaneously achieving high Faradaic efficiency, current density, and stability at low overpotentials is essential for industrial applications of electrochemical CO2 reduction reaction (CO2 RR). However, great challenges still remain in this catalytic process. Herein, a synergistic catalysis strategy is presented to improve CO2 RR performance by anchoring Fe-N sites with cobalt phthalocyanine (denoted as CoPc©Fe-N-C). The potential window of CO Faradaic efficiency above 90% is significantly broadened from 0.18 V over Fe-N-C alone to 0.71 V over CoPc©Fe-N-C while the onset potential of CO2 RR over both catalysts is as low as -0.13 V versus reversible hydrogen electrode. What is more, the maximum CO current density is increased ten times with significantly enhanced stability. Density functional theory calculations suggest that anchored cobalt phthalocyanine promotes the CO desorption and suppresses the competitive hydrogen evolution reaction over Fe-N sites, while the *COOH formation remains almost unchanged, thus demonstrating unprecedented synergistic effect toward CO2 RR.

18.
Angew Chem Int Ed Engl ; 58(45): 16043-16046, 2019 Nov 04.
Artigo em Inglês | MEDLINE | ID: mdl-31468666

RESUMO

Oxidative dehydrogenation of ethane (ODE) is limited by the facile deep oxidation and potential safety hazards. Now, electrochemical ODE reaction is incorporated into the anode of a solid oxide electrolysis cell, utilizing the oxygen species generated at anode to catalytically convert ethane. By infiltrating γ-Al2 O3 onto the surface of La0.6 Sr0.4 Co0.2 Fe0.8 O3-δ -Sm0.2 Ce0.8 O2-δ (LSCF-SDC) anode, the ethylene selectivity reaches as high as 92.5 %, while the highest ethane conversion is up to 29.1 % at 600 °C with optimized current and ethane flow rate. Density functional theory calculations and in situ X-ray photoelectron spectroscopy characterizations reveal that the Al2 O3 /LSCF interfaces effectively reduce the amount of adsorbed oxygen species, leading to improved ethylene selectivity and stability, and that the formation of Al-O-Fe alters the electronic structure of interfacial Fe center with increased density of state around Fermi level and downshift of the empty band, which enhances ethane adsorption and conversion.

19.
Adv Mater ; 31(50): e1901996, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31390100

RESUMO

The unique electronic and structural properties of 2D materials have triggered wide research interest in catalysis. The lattice of 2D materials and the interface between 2D covers and other substrates provide intriguing confinement environments for active sites, which has stimulated a rising area of "confinement catalysis with 2D materials." Fundamental understanding of confinement catalysis with 2D materials will favor the rational design of high-performance 2D nanocatalysts. Confinement catalysis with 2D materials has found extensive applications in energy-related reaction processes, especially in the conversion of small energy-related molecules such as O2 , CH4 , CO, CO2 , H2 O, and CH3 OH. Two representative strategies, i.e., 2D lattice-confined single atoms and 2D cover-confined metals, have been applied to construct 2D confinement catalytic systems with superior catalytic activity and stability. Herein, the recent advances in the design, applications, and structure-performance analysis of two 2D confinement catalytic systems are summarized. The different routes for tuning the electronic states of 2D confinement catalysts are highlighted and perspectives on confinement catalysis with 2D materials toward energy conversion and utilization in the future are provided.

20.
Adv Mater ; 31(50): e1902033, 2019 Dec.
Artigo em Inglês | MEDLINE | ID: mdl-31282069

RESUMO

High-temperature CO2 electrolysis in solid-oxide electrolysis cells (SOECs) could greatly assist in the reduction of CO2 emissions by electrochemically converting CO2 to valuable fuels through effective electrothermal activation of the stable CO bond. If powered by renewable energy resources, it could also provide an advanced energy-storage method for their intermittent output. Compared to low-temperature electrochemical CO2 reduction, CO2 electrolysis in SOECs at high temperature exhibits higher current density and energy efficiency and has thus attracted much recent attention. The history of its development and its fundamental mechanisms, cathode materials, oxygen-ion-conducting electrolyte materials, and anode materials are highlighted. Electrode, electrolyte, and electrode-electrolyte interface degradation issues are comprehensively summarized. Fuel-assisted SOECs with low-cost fuels applied to the anode to decrease the overpotential and electricity consumption are introduced. Furthermore, the challenges and prospects for future research into high-temperature CO2 electrolysis in SOECs are included.

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