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"Tour, James M."
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Urban mining by flash Joule heating
2021
Precious metal recovery from electronic waste, termed urban mining, is important for a circular economy. Present methods for urban mining, mainly smelting and leaching, suffer from lengthy purification processes and negative environmental impacts. Here, a solvent-free and sustainable process by flash Joule heating is disclosed to recover precious metals and remove hazardous heavy metals in electronic waste within one second. The sample temperature ramps to ~3400 K in milliseconds by the ultrafast electrical thermal process. Such a high temperature enables the evaporative separation of precious metals from the supporting matrices, with the recovery yields >80% for Rh, Pd, Ag, and >60% for Au. The heavy metals in electronic waste, some of which are highly toxic including Cr, As, Cd, Hg, and Pb, are also removed, leaving a final waste with minimal metal content, acceptable even for agriculture soil levels. Urban mining by flash Joule heating would be 80× to 500× less energy consumptive than using traditional smelting furnaces for metal-component recovery and more environmentally friendly.
Precious metals recovery from electronics wastes, termed urban mining, is significant for a circular economy. Here, the authors reported a solvent-free and ultrafast process based on flash Joule heating to recover precious metals and remove toxic heavy metals in electronic wastes.
Journal Article
Phase controlled synthesis of transition metal carbide nanocrystals by ultrafast flash Joule heating
2022
Nanoscale carbides enhance ultra-strong ceramics and show activity as high-performance catalysts. Traditional lengthy carburization methods for carbide syntheses usually result in coked surface, large particle size, and uncontrolled phase. Here, a flash Joule heating process is developed for ultrafast synthesis of carbide nanocrystals within 1 s. Various interstitial transition metal carbides (TiC, ZrC, HfC, VC, NbC, TaC, Cr
2
C
3
, MoC, and W
2
C) and covalent carbides (B
4
C and SiC) are produced using low-cost precursors. By controlling pulse voltages, phase-pure molybdenum carbides including β-Mo
2
C and metastable α-MoC
1-x
and η-MoC
1-x
are selectively synthesized, demonstrating the excellent phase engineering ability of the flash Joule heating by broadly tunable energy input that can exceed 3000 K coupled with kinetically controlled ultrafast cooling (>10
4
K s
−1
). Theoretical calculation reveals carbon vacancies as the driving factor for topotactic transition of carbide phases. The phase-dependent hydrogen evolution capability of molybdenum carbides is investigated with β-Mo
2
C showing the best performance.
Nanoscale carbides provide access to ultra-strong ceramics and show activity as high-performance catalysts. Here, the authors report a flash Joule heating process for the ultrafast, general synthesis of various transition metal carbides nanocrystals with phase controllability.
Journal Article
Gram-scale bottom-up flash graphene synthesis
2020
Most bulk-scale graphene is produced by a top-down approach, exfoliating graphite, which often requires large amounts of solvent with high-energy mixing, shearing, sonication or electrochemical treatment
1
–
3
. Although chemical oxidation of graphite to graphene oxide promotes exfoliation, it requires harsh oxidants and leaves the graphene with a defective perforated structure after the subsequent reduction step
3
,
4
. Bottom-up synthesis of high-quality graphene is often restricted to ultrasmall amounts if performed by chemical vapour deposition or advanced synthetic organic methods, or it provides a defect-ridden structure if carried out in bulk solution
4
–
6
. Here we show that flash Joule heating of inexpensive carbon sources—such as coal, petroleum coke, biochar, carbon black, discarded food, rubber tyres and mixed plastic waste—can afford gram-scale quantities of graphene in less than one second. The product, named flash graphene (FG) after the process used to produce it, shows turbostratic arrangement (that is, little order) between the stacked graphene layers. FG synthesis uses no furnace and no solvents or reactive gases. Yields depend on the carbon content of the source; when using a high-carbon source, such as carbon black, anthracitic coal or calcined coke, yields can range from 80 to 90 per cent with carbon purity greater than 99 per cent. No purification steps are necessary. Raman spectroscopy analysis shows a low-intensity or absent D band for FG, indicating that FG has among the lowest defect concentrations reported so far for graphene, and confirms the turbostratic stacking of FG, which is clearly distinguished from turbostratic graphite. The disordered orientation of FG layers facilitates its rapid exfoliation upon mixing during composite formation. The electric energy cost for FG synthesis is only about 7.2 kilojoules per gram, which could render FG suitable for use in bulk composites of plastic, metals, plywood, concrete and other building materials.
Flash Joule heating of inexpensive carbon sources is used to produce gram-scale quantities of high-quality graphene in under a second, without the need for a furnace, solvents or reactive gases.
Journal Article
Laser-induced porous graphene films from commercial polymers
by
Ruiz-Zepeda, Francisco
,
Ye, Ruquan
,
Lin, Jian
in
639/301/1019/1020
,
639/301/357/918
,
639/638/455/941
2014
The cost effective synthesis and patterning of carbon nanomaterials is a challenge in electronic and energy storage devices. Here we report a one-step, scalable approach for producing and patterning porous graphene films with three-dimensional networks from commercial polymer films using a CO
2
infrared laser. The sp
3
-carbon atoms are photothermally converted to sp
2
-carbon atoms by pulsed laser irradiation. The resulting laser-induced graphene (LIG) exhibits high electrical conductivity. The LIG can be readily patterned to interdigitated electrodes for in-plane microsupercapacitors with specific capacitances of >4 mF cm
−2
and power densities of ~9 mW cm
−2
. Theoretical calculations partially suggest that enhanced capacitance may result from LIG’s unusual ultra-polycrystalline lattice of pentagon-heptagon structures. Combined with the advantage of one-step processing of LIG in air from commercial polymer sheets, which would allow the employment of a roll-to-roll manufacturing process, this technique provides a rapid route to polymer-written electronic and energy storage devices.
The straightforward and scalable synthesis and patterning of graphene-based nanomaterials remains a technological challenge. Here, the authors use a CO
2
infrared laser, under ambient conditions, to directly produce and pattern porous graphene films with three-dimensional networks from commercial polymer films.
Journal Article
Atomic cobalt on nitrogen-doped graphene for hydrogen generation
by
Arellano-Jiménez, M. Josefina
,
Zhu, Zhuan
,
Dong Kim, Nam
in
140/146
,
639/301/299
,
639/638/77/886
2015
Reduction of water to hydrogen through electrocatalysis holds great promise for clean energy, but its large-scale application relies on the development of inexpensive and efficient catalysts to replace precious platinum catalysts. Here we report an electrocatalyst for hydrogen generation based on very small amounts of cobalt dispersed as individual atoms on nitrogen-doped graphene. This catalyst is robust and highly active in aqueous media with very low overpotentials (30 mV). A variety of analytical techniques and electrochemical measurements suggest that the catalytically active sites are associated with the metal centres coordinated to nitrogen. This unusual atomic constitution of supported metals is suggestive of a new approach to preparing extremely efficient single-atom catalysts.
There is ongoing interest in the development of non-precious metal catalysts for hydrogen evolution. Here, the authors fabricate a cobalt catalyst in which the cobalt is dispersed as single atoms on nitrogen-doped graphene, and report its high activity and stability for water reduction in acidic media.
Journal Article
Growth of graphene from solid carbon sources
2010
A recipe for success
The past few years have seen spectacular growth of interest in graphene, the carbon monolayer with novel electronic properties. Efforts to produce large sheets of monolayer (or few-layer) graphene could receive a welcome boost from a simple new procedure. Just by baking various solid carbon sources deposited on a metal catalyst substrate at a relatively modest 800 °C, it is possible to produce either pristine graphene or doped graphene in a single step. Suitable starting materials include polymer films and various small molecules.
The past few years have seen a spectacular growth of interest in graphene. Efforts to produce large sheets of monolayer (or few-layer) graphene could receive a welcome boost from the simple procedure reported by these authors. They show how baking various solid carbon sources (for example polymer films) deposited on a metal catalyst substrate can produce either pristine graphene or doped graphene in a single step.
Monolayer graphene was first obtained
1
as a transferable material in 2004 and has stimulated intense activity among physicists, chemists and material scientists
1
,
2
,
3
,
4
. Much research has been focused on developing routes for obtaining large sheets of monolayer or bilayer graphene. This has been recently achieved by chemical vapour deposition (CVD) of CH
4
or C
2
H
2
gases on copper or nickel substrates
5
,
6
,
7
. But CVD is limited to the use of gaseous raw materials, making it difficult to apply the technology to a wider variety of potential feedstocks. Here we demonstrate that large area, high-quality graphene with controllable thickness can be grown from different solid carbon sources—such as polymer films or small molecules—deposited on a metal catalyst substrate at temperatures as low as 800 °C. Both pristine graphene and doped graphene were grown with this one-step process using the same experimental set-up.
Journal Article
High thermal conductivity of suspended few-layer hexagonal boron nitride sheets
by
Haiqing Zhou Jixin Zhu Zheng Liu Zheng Yan Xiujun Fan Jian Lin Gunuk Wang Qingyu Yan Ting Yu Pulickel M. Ajayan James M. Tour
in
Atomic/Molecular Structure and Spectra
,
Biomedicine
,
Biotechnology
2014
The thermal conduction of suspended few-layer hexagonal boron nitride (h-BN) sheets was experimentally investigated using a noncontact micro-Raman spectroscopy method. The first-order temperature coefficients for monolayer (1L), bilayer (2L) and nine-layer (9L) h-BN sheets were measured to be -(3.41 ± 0.12)× 10-2, -(3.15 ± 0.14) × 10-2 and -(3.78 ±0.16)× 10-2 cm-1.K-1, respectively. The room-temperature thermal conductivity of few-layer h-BN sheets was found to be in the range from 227 to 280 W.m-1-K-1, which is comparable to that of bulk h-BN, indicating their potential use as important components to solve heat dissipation problems in thermal management configurations.
Journal Article
High-temperature electrothermal remediation of multi-pollutants in soil
2023
Soil contamination is an environmental issue due to increasing anthropogenic activities. Existing processes for soil remediation suffer from long treatment time and lack generality because of different sources, occurrences, and properties of pollutants. Here, we report a high-temperature electrothermal process for rapid, water-free remediation of multiple pollutants in soil. The temperature of contaminated soil with carbon additives ramps up to 1000 to 3000 °C as needed within seconds via pulsed direct current input, enabling the vaporization of heavy metals like Cd, Hg, Pb, Co, Ni, and Cu, and graphitization of persistent organic pollutants like polycyclic aromatic hydrocarbons. The rapid treatment retains soil mineral constituents while increases infiltration rate and exchangeable nutrient supply, leading to soil fertilization and improved germination rates. We propose strategies for upscaling and field applications. Techno-economic analysis indicates the process holds the potential for being more energy-efficient and cost-effective compared to soil washing or thermal desorption.
Soil contamination is a pressing environmental concern due to increasing anthropogenic activity. Here, the authors developed a rapid and energy-efficient electrothermal process that simultaneously removes heavy metals and organic pollutants in soil.
Journal Article
Low-temperature grapho-epitaxial La-substituted BiFeO3 on metallic perovskite
2024
Bismuth ferrite has garnered considerable attention as a promising candidate for magnetoelectric spin-orbit coupled logic-in-memory. As model systems, epitaxial BiFeO
3
thin films have typically been deposited at relatively high temperatures (650–800 °C), higher than allowed for direct integration with silicon-CMOS platforms. Here, we circumvent this problem by growing lanthanum-substituted BiFeO
3
at 450 °C (which is reasonably compatible with silicon-CMOS integration) on epitaxial BaPb
0.75
Bi
0.25
O
3
electrodes. Notwithstanding the large lattice mismatch between the La-BiFeO
3
, BaPb
0.75
Bi
0.25
O
3
, and SrTiO
3
(001) substrates, all the layers in the heterostructures are well ordered with a [001] texture. Polarization mapping using atomic resolution STEM imaging and vector mapping established the short-range polarization ordering in the low temperature grown La-BiFeO
3
. Current-voltage, pulsed-switching, fatigue, and retention measurements follow the characteristic behavior of high-temperature grown La-BiFeO
3
, where SrRuO
3
typically serves as the metallic electrode. These results provide a possible route for realizing epitaxial multiferroics on complex-oxide buffer layers at low temperatures and opens the door for potential silicon-CMOS integration.
In the field of multiferroic thin films, attaining low-temperature epitaxy has been a long-standing problem. In this work, authors propose a pathway to significantly reduce the BiFeO
3
thin film growth temperature using the BaBiPbO
3
template.
Journal Article
How to control single-molecule rotation
by
Grill, Leonhard
,
Tour, James M.
,
Daniel Boese, A.
in
147/138
,
639/638/542/968
,
639/766/119/544
2019
The orientation of molecules is crucial in many chemical processes. Here, we report how single dipolar molecules can be oriented with maximum precision using the electric field of a scanning tunneling microscope. Rotation is found to occur around a fixed pivot point that is caused by the specific interaction of an oxygen atom in the molecule with the Ag(111) surface. Both directions of rotation are realized at will with 100% directionality. Consequently, the internal dipole moment of an individual molecule can be spatially mapped via its behavior in an applied electric field. The importance of the oxygen-surface interaction is demonstrated by the addition of a silver atom between a single molecule and the surface and the consequent loss of the pivot point.
The orientation of a molecule on a surface affects many processes, so the ability to control single-molecule rotation could be powerful. Here, the authors use the electric field from a scanning tunneling microscope tip to precisely induce unidirectional rotation of a polar molecule, allowing visualization of the molecule’s internal dipole moment.
Journal Article