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Li, Zhe

Publications and source records attributed to Li, Zhe.

At least 55 records · Page 3
All sourcesNASA NTRSDOE OSTI
DOE OSTI2019

Ruthenium-Based Single-Atom Alloy with High Electrocatalytic Activity for Hydrogen Evolution

Highly efficient and stable catalysts for the hydrogen evolution reaction, especially in alkaline conditions are crucial for the practical demands of electrochemical water splitting. Here, the synthesis of a novel RuAu single-atom alloy (SAA) by laser ablation in liquid is reported. The SAA exhibits a high stability and a low overpotential, 24 mV@10 mA cm -2 , which is much lower than that of a Pt/C catalyst (46 mV) in alkaline media. Moreover, the turnover frequency of RuAu SAA is three times that of Pt/C catalyst. Density functional theory computation indicates the excellent catalytic activity of RuAu SAAs originates from the relay catalysis of Ru and Au active sites. This work opens a new avenue toward high-performance SAAs via fast quenching of immiscible metals.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Cobalt-bridged secondary building units in a titanium metal–organic framework catalyze cascade reduction of N-heteroarenes

We report here a novel Ti 3 –BPDC metal–organic framework (MOF) constructed from biphenyl-4,4'-dicarboxylate (BPDC) linkers and Ti 3 (OH) 2 secondary building units (SBUs) with permanent porosity and large 1D channels. Ti–OH groups from neighboring SBUs point toward each other with an O–O distance of 2 Å, and upon deprotonation, act as the first bidentate SBU-based ligands to support Co II -hydride species for effective cascade reduction of N-heteroarenes (such as pyridines and quinolines) via sequential dearomative hydroboration and hydrogenation, affording piperidine and 1,2,3,4-tetrahydroquinoline derivatives with excellent activity (turnover number ~ 1980) and chemoselectivity.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Two-dimensional transition metal carbides as supports for tuning the chemistry of catalytic nanoparticles

Supported nanoparticles are broadly employed in industrial catalytic processes, where the active sites can be tuned by metal-support interactions (MSIs). Although it is well accepted that supports can modify the chemistry of metal nanoparticles, systematic utilization of MSIs for achieving desired catalytic performance is still challenging. The developments of supports with appropriate chemical properties and identification of the resulting active sites are the main barriers. Here, we develop two-dimensional transition metal carbides (MXenes) supported platinum as efficient catalysts for light alkane dehydrogenations. Ordered Pt 3 Ti and surface Pt 3 Nb intermetallic compound nanoparticles are formed via reactive metal-support interactions on Pt/Ti 3 C 2 T x and Pt/Nb 2 CT x catalysts, respectively. MXene supports modulate the nature of the active sites, making them highly selective toward C–H activation. Such exploitation of the MSIs makes MXenes promising platforms with versatile chemical reactivity and tunability for facile design of supported intermetallic nanoparticles over a wide range of compositions and structures.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

A Dynamically Stabilized Single‐Nickel Electrocatalyst for Selective Reduction of Oxygen to Hydrogen Peroxide

Abstract On‐location electrochemical generation of H 2 O 2 is of great current interest. Herein, selective two‐electron reduction of O 2 to H 2 O 2 by a single [Ni II (H 2 O) 6 ] 2+ cation that is dynamically associated with a negatively charged metal–organic layer (MOL) by hydrogen bonding and coulombic interactions is reported. In contrast, Ni II centers covalently immobilized on the MOL reduce O 2 to H 2 O in a four‐ electron process. Oxygen adsorption by [Ni II (H 2 O) 6 ] 2+ followed by two‐electron reduction generates neutral [Ni II (H 2 O) 4 (OH)(OOH)] 0 , which momentarily disconnects from the negatively charged MOL to avoid the injection of additional electrons. Release of H 2 O 2 from [Ni II (H 2 O) 4 (OH)(OOH)] 0 regenerates [Ni II (H 2 O) 6 ] 2+ , which regains affinity to the MOL. Such dynamically associated Ni II single‐metal electrocatalysts ensure high selectivity and represent a new strategy for generating selective catalysts for electrochemical production of important chemicals.

Wang, Tingting↗
DOE OSTI2018

Changes in Catalytic and Adsorptive Properties of 2 nm Pt 3 Mn Nanoparticles by Subsurface Atoms

Supported multimetallic nanoparticles (NPs) are widely used in industrial catalytic processes, where the relation between surface structure and function is well-known. However, the effect of subsurface layers on such catalysts remains mostly unstudied. Here, we demonstrate a clear subsurface effect on supported 2 nm core–shell NPs with atomically precise and high temperature stable Pt 3 Mn intermetallic surface measured by in situ synchrotron X-ray Diffraction, difference X-ray Absorption Spectroscopy, and Energy Dispersive X-ray Spectroscopy. The NPs with a Pt 3 Mn subsurface have 98% selectivity to C–H over C–C bond activation during propane dehydrogenation at 550 °C compared with 82% for core–shell NPs with a Pt subsurface. The difference is correlated with significant reduction in the heats of reactant adsorption due to the Pt3Mn intermetallic subsurface as discerned by theory as well as experiment. The findings of this work highlight the importance of subsurface for supported NP catalysts, which can be tuned via controlled intermetallic formation. Such approach is generally applicable to modifying multimetallic NPs, adding another dimension to the tunability of their catalytic performance.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Modulating Self-Assembly of DNA Crystals with Rationally Designed Agents

This article reports a strategy for controlling the crystallization kinetics and improving the quality of engineered self-assembled 3D DNA crystals. Growing large, high-quality biomacromolecule crystals is critically important for determining the 3D structures of biomacromolecules. It often presents a great challenge to structural biologists. Herein, we introduce a rationally designed agent to modulate the crystallization process. Under such conditions, fewer, but larger, crystals that yield diffraction patterns of modestly higher resolution are produced compared with the crystals from conditions without the modulating agent. We attribute the improvement to a smaller number of nuclei and slow growth rate of crystallization. This strategy is expected to be generally applicable for crystallization of other biomacromolecules.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Creating Zipper‐Like van der Waals Gap Discontinuity in Low‐Temperature‐Processed Nanostructured PbBi 2 n Te 1+3 n : Enhanced Phonon Scattering and Improved Thermoelectric Performance

Abstract Nanoengineered materials can embody distinct atomic structures which deviate from that of the bulk‐grain counterpart and induce significantly modified electronic structures and physical/chemical properties. The phonon structure and thermal properties, which can also be potentially modulated by the modified atomic structure in nanostructured materials, however, are seldom investigated. Employed here is a mild approach to fabricate nanostructured PbBi 2 n Te 1+3 n using a solution‐synthesized PbTe‐Bi 2 Te 3 nano‐heterostructure as a precursor. The as‐obtained monoliths have unprecedented atomic structure, differing from that of the bulk counterpart, especially the zipper‐like van der Waals gap discontinuity and the random arrangement of septuple‐quintuple layers. These structural motifs break the lattice periodicity and coherence of phonon transport, leading to ultralow thermal conductivity and excellent thermoelectric z T .

Xu, Biao↗
DOE OSTI2018

Creating Zipper-Like van der Waals Gap Discontinuity in Low-Temperature-Processed Nanostructured PbBi 2 n Te 1+3 n : Enhanced Phonon Scattering and Improved Thermoelectric Performance

Nanoengineered materials can embody distinct atomic structures which deviate from that of the bulk-grain counterpart and induce significantly modified electronic structures and physical/chemical properties. The phonon structure and thermal properties, which can also be potentially modulated by the modified atomic structure in nanostructured materials, however, are seldom investigated. Employed here is a mild approach to fabricate nanostructured PbBi 2n Te 1+3n using a solution-synthesized PbTe-Bi 2 Te 3 nano-heterostructure as a precursor. The as-obtained monoliths have unprecedented atomic structure, differing from that of the bulk counterpart, especially the zipper-like van der Waals gap discontinuity and the random arrangement of septuple-quintuple layers. These structural motifs break the lattice periodicity and coherence of phonon transport, leading to ultralow thermal conductivity and excellent thermoelectric z T.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Realizing an Epitaxial Decorated Stanene with an Insulating Bandgap

The exploration of intriguing topological quantum physics in stanene has attracted enormous interest but is challenged by lacking desirable material samples. The successful fabrication of monolayer stanene on PbTe(111) films with low-temperature molecular beam epitaxy and thorough characterizations of its atomic and electronic structures are reported here. In situ angle-resolved photoemission spectroscopy together with first-principles calculations identify two hole bands of p xy orbital with a spin-orbit coupling induced band splitting and meanwhile reveal an automatic passivation of p z orbital of stanene. Importantly, material properties are tuned by substrate engineering, realizing a decorated stanene sample with truly insulating bulk on Sr-doped PbTe. In conclusion, this finding paves a road for studies of stanene-based topological quantum effects and electronics.

71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
DOE OSTI2018

Constructing Highly Porous Thermoelectric Monoliths with High-Performance and Improved Portability from Solution-Synthesized Shape-Controlled Nanocrystals

Thermoelectricity offers a viable and reliable solution to convert waste heat into electricity. To enhance the performance and portability of thermoelectric materials, the crystal grain and pore structure should be simultaneously manipulated to achieve high electrical conductivity (σ), low thermal conductivity (κ), high figure of merit (zT), and low relative density. However, they cannot be synchronously realized using nanocrystals with uncontrolled domain size and shape as building blocks. Here, we employ solution-synthesized PbS nanocrystals with large grain size, controllable shape and tunable spatial packing to realize the aforementioned structural tuning. In this work, the as-sintered highly porous and well crystalline monolith exhibits high σ, low κ, high zT (1.06 at 838 K) and low relative density (82%). The phonon transport is studied by density functional theory highlighting the crucial role of phonon–pore scattering in reducing κ to enhance zT. Our strategy may benefit thermoelectrics and shed light on other technical fields such as catalysis, gas sensing, photovoltaics, and so forth.

nanocrystal↗
DOE OSTI2018

Interaction Between Proppant Compaction and Single-/Multiphase Flows in a Hydraulic Fracture

Understanding proppant-transport and -deposition patterns in a hydraulic fracture is vital for effective and economical production of petroleum hydrocarbons. In this research, a numerical-modeling approach, combining the discrete-element method (DEM) with single-/multiphase lattice Boltzmann (LB) simulation, was adopted to advance understanding of the interaction between reservoir depletion, proppant-particle compaction, and single-/multiphase flows in a hydraulic fracture. DEM was used to simulate effective-stress increase and the resultant proppant-particle movement and rearrangement during the process of reservoir depletion caused by hydrocarbon production. Simulated pore structure of the proppant pack was extracted and used as boundary conditions in the LB simulation to calculate the time-dependent permeability of the proppant pack. We first validated the DEM-LB numerical work flow, and the simulated proppant-pack permeabilities as functions of effective stress were in good agreement with laboratory measurements. Furthermore, three proppant packs with the same average particle diameter but different diameter distributions were generated to study the role of proppant-size heterogeneity (variation in particle diameter). Specifically, we used the coefficient of variation (COV) of diameter, defined as the ratio of standard deviation of diameter to mean diameter, to characterize the heterogeneity of particle size. We obtained proppant-pack porosity, permeability, and fracture-width reduction (closure distance) as functions of effective stress. Under the same effective stress, a proppant pack with a higher diameter COV had lower porosity and permeability and larger fracture-width reduction. This was because the high diameter COV gave rise to a wider diameter distribution of proppant particles; smaller particles were compressed into the pore space between larger particles with increasing stress, leading to larger closure distance and lower porosity and permeability. With multiphase LB simulation, relative permeability curves were obtained, which are critical for larger-scale reservoir simulations under various effective stresses. The relative permeability of the oil phase was more sensitive to changes in geometry and stress, compared with the wetting phase. This was because the oil phase occupied larger pores; compaction of the proppant pack affected the structure of the pores, because the pores were farther from the grain contacts and thus more susceptible to collapse. It is also interesting to note that when effective stress increased continuously, oil relative permeability increased first and then decreased. This nonmonotonic behavior was the result of the nonmonotonic development of pore structure and oil connectivity under increasing stress.

Fan, Ming↗
DOE OSTI2018

Manipulating Band Structure through Reconstruction of Binary Metal Sulfide for High‐Performance Thermoelectrics in Solution‐Synthesized Nanostructured Bi 13 S 18 I 2

Abstract Reconstructing canonical binary compounds by inserting a third agent can significantly modify their electronic and phonon structures. Therefore, it has inspired the semiconductor communities in various fields. Introducing this paradigm will potentially revolutionize thermoelectrics as well. Using a solution synthesis, Bi 2 S 3 was rebuilt by adding disordered Bi and weakly bonded I. These new structural motifs and the altered crystal symmetry induce prominent changes in electrical and thermal transport, resulting in a great enhancement of the figure of merit. The as‐obtained nanostructured Bi 13 S 18 I 2 is the first non‐toxic, cost‐efficient, and solution‐processable n‐type material with z T =1.0.

Xu, Biao↗
DOE OSTI2017

On the Dominant Factor Controlling Seasonal Hydrological Forecast Skill in China

Initial conditions (ICs) and climate forecasts (CFs) are the two primary sources of seasonal hydrological forecast skill. However, their relative contribution to predictive skill remains unclear in China. In this study, we investigate the relative roles of ICs and CFs in cumulative runoff (CR) and soil moisture (SM) forecasts using 31-year (1980–2010) ensemble streamflow prediction (ESP) and reverse-ESP (revESP) simulations with the Variable Capacity Infiltration (VIC) hydrologic model. The results show that the relative importance of ICs and CFs largely depends on climate regimes. The influence of ICs is stronger in a dry or wet-to-dry climate regime that covers the northern and western interior regions during the late fall to early summer. In particular, ICs may dominate the forecast skill for up to three months or even six months during late fall and winter months, probably due to the low precipitation value and variability in the dry period. In contrast, CFs become more important for most of southern China or during summer months. The impact of ICs on SM forecasts tends to cover larger domains than on CR forecasts. These findings will greatly benefit future work that will target efforts towards improving current forecast levels for the particular regions and forecast periods.

54 ENVIRONMENTAL SCIENCES↗
DOE OSTI2017

Enhancing charge mobilities in organic semiconductors by selective fluorination: a design approach based on a quantum mechanical perspective

Selective fluorination of organic semiconducting molecules is proposed as a means to achieving enhanced hole mobility. Naphthalene is examined here as a root molecular system with fluorination performed at various sites. Our quantum chemical calculations show that selective fluorination can enhance attractive intermolecular interactions while reducing charge trapping. Those observations suggest a design principle whereby fluorination is utilized for achieving high charge mobilities in the crystalline form. The utility of this design principle is demonstrated through an application to perylene, which is an important building block of organic semiconducting materials. We also show that a quantum mechanical perspective of nuclear degrees of freedom is crucial for a reliable description of charge transport.

36 MATERIALS SCIENCE↗