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1.
J Phys Condens Matter ; 32(1): 015402, 2020 Jan 01.
Artigo em Inglês | MEDLINE | ID: mdl-31505475

RESUMO

Much effort has been devoted to the investigation of the physical and chemical properties of the Au-O system over a range of pressures, owing to the considerable importance of these materials in fundamental and practical applications. To date, however, only Au1+, Au2+, Au3+, and Au5+ oxidation states have been identified in the Au-O system, but tetravalent Au4+ has not been found. Here, we report the results of structure prediction for the Au-O system at high pressure via the effective structure prediction methodology within a first-principles electronic structure framework. We have uncovered an intriguing structure with AuO2 composition and tetravalent Au, stable at high pressures. This phase shows an electronic transition from a metal to a semiconducting phase as a function of pressure. The present results provide fundamental understanding of the structural and physicochemical properties of compressed Au-O compounds.

2.
Nano Lett ; 19(9): 6461-6465, 2019 Sep 11.
Artigo em Inglês | MEDLINE | ID: mdl-31434487

RESUMO

The concept of the memristor, a resistor with memory, was proposed by Chua in 1971 as the fourth basic element of electric circuitry. Despite a significant amount of effort devoted to the understanding of memristor theory, our understanding of the nonpinched current-voltage (I-V) hysteresis loop in memristors remains incomplete. Here we propose a physical model of a memristor, with a capacitor connected in parallel, which explains how the nonpinched I-V hysteresis behavior originates from the capacitive-coupled memristive effect. Our model replicates eight types of characteristic nonlinear I-V behavior, which explains all observed nonpinched I-V curves seen in experiments. Furthermore, a reversible transition from a nonpinched I-V hysteresis loop to an ideal pinched I-V hysteresis loop is found, which explains the experimental data obtained in C15H11O6-based devices when subjected to an external stimulus (e.g., voltage, moisture, or temperature). Our results provide the vital physics models and materials insights for elucidating the origins of nonpinched I-V hysteresis loops ascribed to capacitive-coupled memristive behavior.

3.
Phys Chem Chem Phys ; 21(32): 17621-17627, 2019 Aug 15.
Artigo em Inglês | MEDLINE | ID: mdl-31347635

RESUMO

In addition to the known Au3+ and Au5+, it has recently been shown that Au is likely to possess unusual valence states in compressed Au-F compounds. However, our simulations reveal that polymeric ground-state AuF4 shows an unexpected 6-fold coordination rather than a 4-fold one, indicating that more complete comprehending on the anomalous Au4+ is highly required. To fully understand the nature and origin of anomalous valence states in Au, we have extensively investigated the ground-state structures of Au-F compounds at high pressures using quantum mechanical computational methods. As a consequence, we identify several previously unreported (stable) AuF2, AuF3 and AuF4 structures. Our results extend the known polymorphism of AuFn compounds and offer a fundamental understanding of the origin of unusual valence states in Au that prevail at high pressure.

4.
Phys Chem Chem Phys ; 21(23): 12389-12395, 2019 Jun 21.
Artigo em Inglês | MEDLINE | ID: mdl-31140490

RESUMO

We report the amorphization of three metal-organic frameworks, ZIF-4, ZIF-62, and ZIF-zni, by synchrotron X-ray radiation. Complete amorphization of these structures occurs on timescales ranging from minutes to hours. This process is non-isokinetic in all three cases, given a varying transformation rate as the transformation proceeds. The underlying mechanism bears the signature of inhomogeneous nucleation, reflected by an increasing local Avrami exponent over time. Furthermore, the amorphization rate accelerates with increasing temperature, even far below the usual thermal stability limit of each crystalline phase. These results not only have important implications for interpretation of X-ray synchrotron studies on the stability of metal-organic frameworks, they also shed light on the rarely-discussed and generally unpredictable experimental problem of beam damage in organic and inorganic compounds in general.

5.
J Am Chem Soc ; 141(23): 9330-9337, 2019 Jun 12.
Artigo em Inglês | MEDLINE | ID: mdl-31117654

RESUMO

We present an in situ powder X-ray diffraction study on the phase stability and polymorphism of the metal-organic framework ZIF-4, Zn(imidazolate)2, at simultaneous high pressure and high temperature, up to 8 GPa and 600 °C. The resulting pressure-temperature phase diagram reveals four, previously unknown, high-pressure-high-temperature ZIF phases. The crystal structures of two new phases-ZIF-4-cp-II and ZIF-hPT-II-were solved by powder diffraction methods. The total energy of ZIF-4-cp-II was evaluated using density functional theory calculations and was found to lie in between that of ZIF-4 and the most thermodynamically stable polymorph, ZIF- zni. ZIF-hPT-II was found to possess a doubly interpenetrated diamondoid topology and is isostructural with previously reported Cd(Imidazolate)2 and Hg(Imidazolate)2 phases. This phase exhibited extreme resistance to both temperature and pressure. The other two new phases could be assigned with a unit cell and space group, although their structures remain unknown. The pressure-temperature phase diagram of ZIF-4 is strikingly complicated when compared with that of the previously investigated, closely related ZIF-62 and demonstrates the ability to traverse complex energy landscapes of metal-organic systems using the combined application of pressure and temperature.

6.
Nanoscale ; 11(17): 8260-8269, 2019 Apr 25.
Artigo em Inglês | MEDLINE | ID: mdl-30976766

RESUMO

The successful fabrication of black phosphorene (Black-P) in 2014 and subsequent synthesis of layered black As1-xPx alloys have inspired research into two-dimensional (2D) binary As-P compounds. The very recent success in growing blue phosphorene (Blue-P) further motivated exploration of 2D Blue-AsP materials. Here, using ab initio swarm-intelligence global minimum structure-searching methods, we have obtained a series of novel and energetically favored 2D Blue-AsP (denoted x-AsP, x = I, II, III, IV, V) compounds with As : P = 1 : 1 stoichiometry. They display similar honeycomb structures to Blue-P. Remarkably, the lowest-energy AsP monolayer, namely I-AsP, not only possesses a quasi-direct band gap (2.41 eV), which can be tuned to a direct and optimal gap for photovoltaic applications by in-plane strain, but also has an ultrahigh electronic mobility up to ∼7.4 × 104 cm2 V-1 s-1, far surpassing that of Blue-P, and also exhibits high absorption coefficients (×105 cm-1). Our simulations also show that 30 nm-thick I-AsP sheet-based cells have photovoltaic efficiency as high as ∼12%, and the I-AsP/CdSe heterostructure solar cells possess a power conversion efficiency as high as ∼13%. All these outstanding characteristics suggest the I-AsP sheet as a promising material for high-efficiency solar cells.

7.
Nat Commun ; 10(1): 999, 2019 03 01.
Artigo em Inglês | MEDLINE | ID: mdl-30824710

RESUMO

Stimuli-responsive behaviors of flexible metal-organic frameworks (MOFs) make these materials promising in a wide variety of applications such as gas separation, drug delivery, and molecular sensing. Considerable efforts have been made over the last decade to understand the structural changes of flexible MOFs in response to external stimuli. Uniform pore deformation has been used as the general description. However, recent advances in synthesizing MOFs with non-uniform porous structures, i.e. with multiple types of pores which vary in size, shape, and environment, challenge the adequacy of this description. Here, we demonstrate that the CO2-adsorption-stimulated structural change of a flexible MOF, ZIF-7, is induced by CO2 migration in its non-uniform porous structure rather than by the proactive opening of one type of its guest-hosting pores. Structural dynamics induced by guest migration in non-uniform porous structures is rare among the enormous number of MOFs discovered and detailed characterization is very limited in the literature. The concept presented in this work provides new insights into MOF flexibility.

8.
Nat Mater ; 18(4): 370-376, 2019 04.
Artigo em Inglês | MEDLINE | ID: mdl-30886398

RESUMO

Metal-organic frameworks (MOFs) are microporous materials with huge potential for chemical processes. Structural collapse at high pressure, and transitions to liquid states at high temperature, have recently been observed in the zeolitic imidazolate framework (ZIF) family of MOFs. Here, we show that simultaneous high-pressure and high-temperature conditions result in complex behaviour in ZIF-62 and ZIF-4, with distinct high- and low-density amorphous phases occurring over different regions of the pressure-temperature phase diagram. In situ powder X-ray diffraction, Raman spectroscopy and optical microscopy reveal that the stability of the liquid MOF state expands substantially towards lower temperatures at intermediate, industrially achievable pressures and first-principles molecular dynamics show that softening of the framework coordination with pressure makes melting thermodynamically easier. Furthermore, the MOF glass formed by melt quenching the high-temperature liquid possesses permanent, accessible porosity. Our results thus imply a route to the synthesis of functional MOF glasses at low temperatures, avoiding decomposition on heating at ambient pressure.

9.
Phys Chem Chem Phys ; 20(46): 29472-29479, 2018 Nov 28.
Artigo em Inglês | MEDLINE | ID: mdl-30456400

RESUMO

Transition metal dichalcogenides have attracted significant attention due to both fundamental interest and their potential applications. Here, we have systematically explored the crystal structures of ReX2 (X = S, Se, and Te) over the pressure range of 0-300 GPa, employing swarm-intelligence-based structure prediction methodology. Several new structures are found to be stable at high pressures. The calculated enthalpy of formation suggested that all predicted high-pressure structures are stable against decomposition into elemental end-members. Moreover, we found that the simulated X-ray diffraction patterns of ReSe2 are in good agreement with experimental data. Pressure-induced metallization of ReX2 has been revealed from the analysis of its electronic structure. Our electron-phonon coupling calculations indicate ReSe2 and ReTe2 are superconducting phases at high pressures.

10.
Nat Commun ; 9(1): 4506, 2018 10 29.
Artigo em Inglês | MEDLINE | ID: mdl-30374042

RESUMO

Metal halide perovskites (MHPs) are of great interest for optoelectronics because of their high quantum efficiency in solar cells and light-emitting devices. However, exploring an effective strategy to further improve their optical activities remains a considerable challenge. Here, we report that nanocrystals (NCs) of the initially nonfluorescent zero-dimensional (0D) cesium lead halide perovskite Cs4PbBr6 exhibit a distinct emission under a high pressure of 3.01 GPa. Subsequently, the emission intensity of Cs4PbBr6 NCs experiences a significant increase upon further compression. Joint experimental and theoretical analyses indicate that such pressure-induced emission (PIE) may be ascribed to the enhanced optical activity and the increased binding energy of self-trapped excitons upon compression. This phenomenon is a result of the large distortion of [PbBr6]4- octahedral motifs resulting from a structural phase transition. Our findings demonstrate that high pressure can be a robust tool to boost the photoluminescence efficiency and provide insights into the relationship between the structure and optical properties of 0D MHPs under extreme conditions.

11.
J Am Chem Soc ; 140(42): 13970-13975, 2018 Oct 24.
Artigo em Inglês | MEDLINE | ID: mdl-30265807

RESUMO

Pressure quenching of optical emission largely limits the potential application of many materials in optical pressure-sensing devices, since emission intensity is crucially connected to performance. Boosting visible-light emission at high pressure is, therefore, an important goal. Here, we demonstrate that the emission of CdSe nanocrystals (NCs) can be enhanced by more than an order of magnitude by compression. The brightest emission can be achieved at pressures corresponding to the phase transitions in different sized CdSe NCs. Very bright blue emission can be obtained by exploiting the increase in band gap with increasing pressure. First-principles calculations indicate that the interaction between the capping oleic acid (OA) layer and the CdSe core is strengthened with increased Hirshfeld charge at high pressure. The effective surface reconstruction associated with the removal of surface-related trap states is highly responsible for the pressure-induced emission enhancement of these CdSe NCs. These findings pave the way for designing a stress nanogauge with easy optical readout and provide a route for tuning bright-fluorescence imaging in response to an externally applied pressure.

12.
J Phys Chem Lett ; 9(19): 5785-5791, 2018 Oct 04.
Artigo em Inglês | MEDLINE | ID: mdl-30145904

RESUMO

In the past decade, the group V-VI compounds have been widely investigated due to their excellent properties and applications. It is now accepted that diverse stoichiometry can yield new compounds with unanticipated properties, uncovering potentially new physicochemical mechanisms. However, in this group, aside from the conventional A2B3-type, no other energetically stable stoichiometry has been reported yet. Here, we report that Bi2S3 is unstable and decomposes into stoichiometric BiS2 and BiS with different Bi valence states upon compression. Encouragingly, we successfully synthesized the predicted BiS2 phase and thus, confirmed its existence. Our current calculations reveal that the found BiS2 phase is a semimetal, associated with the increased concentration of nonmetallic S. The present results represent the first counterintuitive stable stoichiometry of group V-VI and provide a good example in designing and synthesizing new compounds under compression.

13.
Adv Mater ; 30(31): e1800676, 2018 Aug.
Artigo em Inglês | MEDLINE | ID: mdl-29920795

RESUMO

Highly active, stable, and cheap Pt-free catalysts for the hydrogen evolution reaction (HER) are facing increasing demand as a result of their potential use in future energy-conversion systems. However, the development of HER electrocatalysts with Pt-like or even superior activity, in particular ones that can function under alkaline conditions, remains a significant challenge. Here, the synthesis of a novel carbon-loaded ruthenium nanoparticle electrocatalyst (Ru@CQDs) for the HER, using carbon quantum dots (CQDs), is reported. Electrochemical tests reveal that, even under extremely alkaline conditions (1 m KOH), the as-formed Ru@CQDs exhibits excellent catalytic behavior with an onset overpotential of 0 mV, a Tafel slope of 47 mV decade-1 , and good durability. Most importantly, it only requires an overpotential of 10 mV to achieve the current density of 10 mA cm-2 . Such catalytic characteristics are superior to the current commercial Pt/C and most noble metals, non-noble metals, and nonmetallic catalysts under basic conditions. These findings open a new field for the application of CQDs and add to the growing family of metal@CQDs with high HER performance.

14.
Nat Commun ; 9(1): 722, 2018 02 19.
Artigo em Inglês | MEDLINE | ID: mdl-29459672

RESUMO

Polymeric nitrogen, stabilized by compressing pure molecular nitrogen, has yet to be recovered to ambient conditions, precluding its application as a high-energy density material. Here we suggest a route for synthesis of a tetragonal polymeric nitrogen, denoted t-N, via He-N compounds at high pressures. Using first-principles calculations with structure searching, we predict a class of nitrides with stoichiometry HeN4 that are energetically stable (relative to a mixture of solid He and N2) above 8.5 GPa. At high pressure, HeN4 comprises a polymeric channel-like nitrogen framework filled with linearly arranged helium atoms. The nitrogen framework persists to ambient pressure on decompression after removal of helium, forming pure polymeric nitrogen, t-N. t-N is dynamically and mechanically stable at ambient pressure with an estimated energy density of ~11.31 kJ/g, marking it out as a remarkable high-energy density material. This expands the known polymeric forms of nitrogen and indicates a route to its synthesis.

15.
Adv Mater ; 30(9)2018 Mar.
Artigo em Inglês | MEDLINE | ID: mdl-29333763

RESUMO

Cesium-based trihalide perovskites have been demonstrated as promising light absorbers for photovoltaic applications due to their superb composition stability. However, the large energy losses (Eloss ) observed in inorganic perovskite solar cells has become a major hindrance impairing the ultimate efficiency. Here, an effective and reproducible method of modifying the interface between a CsPbI2 Br absorber and polythiophene hole-acceptor to minimize the Eloss is reported. It is demonstrated that polythiophene, deposited on the top of CsPbI2 Br, can significantly reduce electron-hole recombination within the perovskite, which is due to the electronic passivation of surface defect states. In addition, the interfacial properties are improved by a simple annealing process, leading to significantly reduced energy disorder in polythiophene and enhanced hole-injection into the hole-acceptor. Consequently, one of the highest power conversion efficiency (PCE) of 12.02% from a reverse scan in inorganic mixed-halide perovskite solar cells is obtained. Modifying the perovskite films with annealing polythiophene enables an open-circuit voltage (VOC ) of up to 1.32 V and Eloss of down to 0.5 eV, which both are the optimal values reported among cesium-lead mixed-halide perovskite solar cells to date. This method provides a new route to further improve the efficiency of perovskite solar cells by minimizing the Eloss .

16.
Angew Chem Int Ed Engl ; 57(9): 2393-2398, 2018 02 23.
Artigo em Inglês | MEDLINE | ID: mdl-29356331

RESUMO

Polymer carbon dots (PCDs) are proposed as a new class of room-temperature phosphorescence (RTP) materials. The abundant energy levels in PCDs increase the probability of intersystem crossing (ISC) and their covalently crosslinked framework structures greatly suppress the nonradiative transitions. The efficient methods allow the manufacture of PCDs with unique RTP properties in air without additional metal complexation or complicated matrix composition. They thus provide a route towards the rational design of metal-free RTP materials that may be synthesized easily. Furthermore, we find that RTP is associated with a crosslink-enhanced emission (CEE) effect, which provides further routes to design improved PCDs with diverse RTP performance. Our results show the potential of PCDs as a universal route to achieve effective metal-free RTP.

17.
Phys Rev Lett ; 121(25): 255703, 2018 Dec 21.
Artigo em Inglês | MEDLINE | ID: mdl-30608845

RESUMO

There is compelling geochemical evidence for primordial helium trapped in Earth's lower mantle, but the origin and nature of the helium source remain elusive due to scarce knowledge on viable helium-bearing compounds that are extremely rare. Here we explore materials physics underlying this prominent challenge. Our structure searches in conjunction with first-principles energetic and thermodynamic calculations uncover a remarkable helium-bearing compound FeO_{2}He at high pressure-temperature conditions relevant to the core-mantle boundary. Calculated sound velocities consistent with seismic data validate FeO_{2}He as a feasible constituent in ultralow velocity zones at the lowermost mantle. These mutually corroborating findings establish the first and hitherto only helium-bearing compound viable at pertinent geophysical conditions, thus providing vital physics mechanisms and materials insights for elucidating the enigmatic helium reservoir in deep Earth.

18.
Sci Rep ; 7(1): 11111, 2017 09 11.
Artigo em Inglês | MEDLINE | ID: mdl-28894256

RESUMO

Electrocaloric (EC) materials show promise in eco-friendly solid-state refrigeration and integrable on-chip thermal management. While direct measurement of EC thin-films still remains challenging, a generic theoretical framework for quantifying the cooling properties of rich EC materials including normal-, relaxor-, organic- and anti-ferroelectrics is imperative for exploiting new flexible and room-temperature cooling alternatives. Here, we present a versatile theory that combines Master equation with Maxwell relations and analytically relates the macroscopic cooling responses in EC materials with the intrinsic diffuseness of phase transitions and correlation characteristics. Under increased electric fields, both EC entropy and adiabatic temperature changes increase quadratically initially, followed by further linear growth and eventual gradual saturation. The upper bound of entropy change (∆Smax) is limited by distinct correlation volumes (V cr ) and transition diffuseness. The linearity between V cr and the transition diffuseness is emphasized, while ∆Smax = 300 kJ/(K.m3) is obtained for Pb0.8Ba0.2ZrO3. The ∆Smax in antiferroelectric Pb0.95Zr0.05TiO3, Pb0.8Ba0.2ZrO3 and polymeric ferroelectrics scales proportionally with V cr-2.2, owing to the one-dimensional structural constraint on lattice-scale depolarization dynamics; whereas ∆Smax in relaxor and normal ferroelectrics scales as ∆Smax ~ V cr-0.37, which tallies with a dipolar interaction exponent of 2/3 in EC materials and the well-proven fractional dimensionality of 2.5 for ferroelectric domain walls.

19.
Inorg Chem ; 56(13): 7449-7453, 2017 Jul 03.
Artigo em Inglês | MEDLINE | ID: mdl-28598603

RESUMO

Using global structure searches, we have explored the structural stability of CaB3N3, a compound analogous to CaC6, under pressure. There are two high-pressure phases with space groups R3c and Amm2 that were found to be stable between 29 and 42 GPa, and above 42 GPa, respectively. The two phases show different structural frameworks, analogous to graphitic CaC6. Phonon calculations confirm that both structures are also dynamically stable at high pressures. The electronic structure calculations show that the R3c phase is a semiconductor with a band gap of 2.21 eV and that the Amm2 phase is a semimetal. These findings help advance our understanding of the Ca-B-N ternary system.

20.
J Am Chem Soc ; 138(10): 3484-92, 2016 Mar 16.
Artigo em Inglês | MEDLINE | ID: mdl-26885940

RESUMO

Crystalline solids dominate the field of metal-organic frameworks (MOFs), with access to the liquid and glass states of matter usually prohibited by relatively low temperatures of thermal decomposition. In this work, we give due consideration to framework chemistry and topology to expand the phenomenon of the melting of 3D MOFs, linking crystal chemistry to framework melting temperature and kinetic fragility of the glass-forming liquids. Here we show that melting temperatures can be lowered by altering the chemistry of the crystalline MOF state, which provides a route to facilitate the melting of other MOFs. The glasses formed upon vitrification are chemically and structurally distinct from the three other existing categories of melt-quenched glasses (inorganic nonmetallic, organic, and metallic), and retain the basic metal-ligand connectivity of crystalline MOFs, which connects their mechanical properties to their starting chemical composition. The transfer of functionality from crystal to glass points toward new routes to tunable, functional hybrid glasses.

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