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"Warner, Jamie H"
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General synthesis of high-entropy single-atom nanocages for electrosynthesis of ammonia from nitrate
by
Tang, Sishuang
,
Wang, Maoyu
,
Guan, Weixin
in
639/301/299/886
,
639/638/161/886
,
704/172/169/896
2024
Given the growing emphasis on energy efficiency, environmental sustainability, and agricultural demand, there’s a pressing need for decentralized and scalable ammonia production. Converting nitrate ions electrochemically, which are commonly found in industrial wastewater and polluted groundwater, into ammonia offers a viable approach for both wastewater treatment and ammonia production yet limited by low producibility and scalability. Here we report a versatile and scalable solution-phase synthesis of high-entropy single-atom nanocages (HESA NCs) in which Fe and other five metals-Co, Cu, Zn, Cd, and In-are isolated via cyano-bridges and coordinated with C and N, respectively. Incorporating and isolating the five metals into the matrix of Fe resulted in Fe-C
5
active sites with a minimized symmetry of lattice as well as facilitated water dissociation and thus hydrogenation process. As a result, the Fe-HESA NCs exhibited a high selectivity toward NH
3
from the electrocatalytic reduction of nitrate with a Faradaic efficiency of 93.4% while maintaining a high yield rate of 81.4 mg h
−1
mg
−1
.
Converting nitrate from waste sources into ammonia provides an effective method for both wastewater treatment and ammonia production. Here the authors report a scalable solution-phase synthesis of high-entropy single-atom nanocage catalysts for efficient nitrate-to-ammonia conversion.
Journal Article
Dislocation-Driven Deformations in Graphene
by
Warner, Jamie H.
,
Margine, Elena Roxana
,
Robertson, Alexander W.
in
Atomic structure
,
Atoms
,
Carbon
2012
The movement of dislocations in a crystal is the key mechanism for plastic deformation in all materials. Studies of dislocations have focused on three-dimensional materials, and there is little experimental evidence regarding the dynamics of dislocations and their impact at the atomic level on the lattice structure of graphene. We studied the dynamics of dislocation pairs in graphene, recorded with single-atom sensitivity. We examined stepwise dislocation movement along the zig-zag lattice direction mediated either by a single bond rotation or through the loss of two carbon atoms. The strain fields were determined, showing how dislocations deform graphene by elongation and compression of C-C bonds, shear, and lattice rotations.
Journal Article
Atomic electrostatic maps of 1D channels in 2D semiconductors using 4D scanning transmission electron microscopy
by
Han, Grace G. D.
,
Warner, Jamie H.
,
Allen, Christopher S.
in
147/137
,
147/143
,
639/301/357/1018
2019
Defects in materials give rise to fluctuations in electrostatic fields that reflect the local charge density, but imaging this with single atom sensitivity is challenging. However, if possible, this provides information about the energetics of adatom binding, localized conduction channels, molecular functionality and their relationship to individual bonds. Here, ultrastable electron-optics are combined with a high-speed 2D electron detector to map electrostatic fields around individual atoms in 2D monolayers using 4D scanning transmission electron microscopy. Simultaneous imaging of the electric field, phase, annular dark field and the total charge in 2D MoS
2
and WS
2
is demonstrated for pristine areas and regions with 1D wires. The in-gap states in sulphur line vacancies cause 1D electron-rich channels that are mapped experimentally and confirmed using density functional theory calculations. We show how electrostatic fields are sensitive in defective areas to changes of atomic bonding and structural determination beyond conventional imaging.
Imaging electrostatic field around individual atoms or defective areas in monolayer 2D materials is crucial to understand their structural coordination. Here, the authors report local changes in specific atomic bonds and provide in-depth structural information of complex defective monolayer MoS
2
and WS
2
systems by 4D STEM.
Journal Article
Spatial control of defect creation in graphene at the nanoscale
by
Warner, Jamie H.
,
Olivier, Jaco
,
Allen, Christopher S.
in
639/301/357/918
,
Humanities and Social Sciences
,
Irradiation
2012
Defects in graphene alter its electrical, chemical, magnetic and mechanical properties. The intentional creation of defects in graphene offers a means for engineering its properties. Techniques such as ion irradiation intentionally induce atomic defects in graphene, for example, divacancies, but these defects are randomly scattered over large distances. Control of defect formation with nanoscale precision remains a significant challenge. Here we show control over both the location and average complexity of defect formation in graphene by tailoring its exposure to a focussed electron beam. Divacancies and larger disordered structures are produced within a 10 × 10 nm
2
region of graphene and imaged after creation using an aberration-corrected transmission electron microscope. Some of the created defects were stable, whereas others relaxed to simpler structures through bond rotations and surface adatom incorporation. These results are important for the utilization of atomic defects in graphene-based research.
Intentional defect creation in graphene is key to engineering its electrical, chemical, magnetic and mechanical properties. Robertson
et al
. create defects by electron beam irradiation with sub-knock-on damage threshold, and show control over the defect position at the nanoscale and over the defect complexity.
Journal Article
Atomic structure and defect dynamics of monolayer lead iodide nanodisks with epitaxial alignment on graphene
2020
Lead Iodide (PbI
2
) is a large bandgap 2D layered material that has potential for semiconductor applications. However, atomic level study of PbI
2
monolayer has been limited due to challenges in obtaining thin crystals. Here, we use liquid exfoliation to produce monolayer PbI
2
nanodisks (30-40 nm in diameter and > 99% monolayer purity) and deposit them onto suspended graphene supports to enable atomic structure study of PbI
2
. Strong epitaxial alignment of PbI
2
monolayers with the underlying graphene lattice occurs, leading to a phase shift from the 1 T to 1 H structure to increase the level of commensuration in the two lattice spacings. The fundamental point vacancy and nanopore structures in PbI
2
monolayers are directly imaged, showing rapid vacancy migration and self-healing. These results provide a detailed insight into the atomic structure of monolayer PbI
2
, and the impact of the strong van der Waals interaction with graphene, which has importance for future applications in optoelectronics.
Imaging liquid phase exfoliated nanosheets on suspended graphene via annular dark-field STEM can enable identification of various defects, vacancies and their migration. Here, the authors report matching of zigzag edges of monolayer PbI2 with graphene arm-chairs leading to a phase shift from 1 T to 1 H structure to maximize commensuration of the lattices.
Journal Article
Electrically tunable organic–inorganic hybrid polaritons with monolayer WS2
by
Warner, Jamie H.
,
Taylor, Robert A.
,
Flatten, Lucas C.
in
639/301/357/1018
,
639/624/1075/401
,
639/624/399/1097
2017
Exciton-polaritons are quasiparticles consisting of a linear superposition of photonic and excitonic states, offering potential for nonlinear optical devices. The excitonic component of the polariton provides a finite Coulomb scattering cross section, such that the different types of exciton found in organic materials (Frenkel) and inorganic materials (Wannier-Mott) produce polaritons with different interparticle interaction strength. A hybrid polariton state with distinct excitons provides a potential technological route towards
in situ
control of nonlinear behaviour. Here we demonstrate a device in which hybrid polaritons are displayed at ambient temperatures, the excitonic component of which is part Frenkel and part Wannier-Mott, and in which the dominant exciton type can be switched with an applied voltage. The device consists of an open microcavity containing both organic dye and a monolayer of the transition metal dichalcogenide WS
2
. Our findings offer a perspective for electrically controlled nonlinear polariton devices at room temperature.
Hybrid polariton states originating from the strong coupling of photonic and excitonic states hold promise for control of nonlinear light behaviour. Here, the authors fabricate a microcavity containing organic dye and WS
2
, featuring hybrid polaritons arising from both Frenkel and Wannier-Mott excitons.
Journal Article
Waterproof molecular monolayers stabilize 2D materials
2019
Two-dimensional van der Waals materials have rich and unique functional properties, but many are susceptible to corrosion under ambient conditions. Here we show that linear alkylamines n-Cm
H2m+1NH₂, with m = 4 through 11, are highly effective in protecting the optoelectronic properties of these materials, such as black phosphorus (BP) and transition-metal dichalcogenides (TMDs: WS₂, 1T′-MoTe₂, WTe₂, WSe₂, TaS₂, and NbSe₂). As a representative example, n-hexylamine (m = 6) can be applied in the form of thin molecular monolayers on BP flakes with less than 2-nm thickness and can prolong BP’s lifetime from a few hours to several weeks and even months in ambient environments. Characterizations combined with our theoretical analysis show that the thin monolayers selectively sift out water molecules, forming a drying layer to achieve the passivation of the protected 2D materials. The monolayer coating is also stable in air, H₂ annealing, and organic solvents, but can be removed by certain organic acids.
Journal Article
Graphene : fundamentals and emergent applications
by
Warner, Jamie H.
,
Rümmeli, Mark H.
,
Bachmatiuk, Alicja
in
Graphene
,
Graphene - Industrial applications
2013,2012
Providing fundamental knowledge necessary to understand graphene's atomic structure, band-structure, unique properties and an overview of groundbreaking current and emergent applications, this new handbook is essential reading for materials scientists, chemists and physicists.Since the 2010 physics Nobel Prize awarded to Geim and Novosolev for.
Growth of carbon nanotubes via twisted graphene nanoribbons
by
Warner, Jamie H.
,
Shinohara, Hisanori
,
Nishimoto, Yoshio
in
639/301/930/1032
,
639/925/357/73
,
639/925/357/918
2013
Carbon nanotubes have long been described as rolled-up graphene sheets. It is only fairly recently observed that longitudinal cleavage of carbon nanotubes, using chemical, catalytical and electrical approaches, unzips them into thin graphene strips of various widths, the so-called graphene nanoribbons. In contrast, rolling up these flimsy ribbons into tubes in a real experiment has not been possible. Theoretical studies conducted by Kit
et al
. recently demonstrated the tube formation through twisting of graphene nanoribbon, an idea very different from the rolling-up postulation. Here we report the first experimental evidence of a thermally induced self-intertwining of graphene nanoribbons for the preferential synthesis of (7, 2) and (8, 1) tubes within parent-tube templates. Through the tailoring of ribbon’s width and edge, the present finding adds a radically new aspect to the understanding of carbon nanotube formation, shedding much light on not only the future chirality tuning, but also contemporary nanomaterials engineering.
Carbon nanotubes can be considered as rolled-up small sheets of graphene. Here Lim and colleagues demonstrate this process, by fabricating carbon nanotubes through a thermally induced process of self-intertwining of graphene nanoribbons.
Journal Article
Dynamic Ionic Environment Modulation for Precise Electrosynthesis of Heterostructured Bimetallic Nanoparticles
2025
Bimetallic heterostructures, including core–shell and Janus configurations, often offer unique electrocatalytic properties compared to monometallic nanoparticles. However, achieving precise control over both elemental composition and spatial arrangement within these structures remains a challenge. Here, an electrosynthesis method is introduced that enables the fabrication of heterostructured bimetallic nanoparticles with precise, independent control of their elemental distribution. By leveraging dual‐channel scanning electrochemical cell microscopy (SECCM), the local ionic environment is dynamically modulated in situ, adjusting the deposition bias between channels to achieve selective electrodeposition. This approach allows temporal control over the solution conditions within the SECCM droplet, facilitating the synthesis of multi‐layer core–shell nanoparticles with tunable thickness, number, and sequence of layers. This technique is demonstrated with Pt–Cu and Pt–Ni systems, synthesizing arrays of Cu@Pt and Pt@Cu core–shell structures, which are then screened for catalytic activity in hydrogen evolution (HER) and oxygen reduction (ORR) reactions. The high spatial resolution and on‐demand control over the composition and structure make this method well‐suitable for creating arrays of complex, multi‐metallic heterostructures, which is expected to accelerate the discovery of advanced electrocatalytic materials, offering a platform for efficient and scalable electrocatalyst screening. An electrosynthesis method is introduced for fabricating heterostructured bimetallic nanoparticles, providing precise and independent control over elemental distribution within individual nanostructures. By dynamically modulating the ionic environment in a dual‐channel nanopipette using scanning electrochemical cell microscopy, core–shell nanoparticles with customizable elemental hierarchy and thickness are achieved. The synthesized nanoparticles are readily screened for their electrocatalytic activities.
Journal Article