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3,161
result(s) for
"Aziz, J."
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A metal-free organic–inorganic aqueous flow battery
by
Galvin, Cooper J.
,
Marshak, Michael P.
,
Gerhardt, Michael R.
in
639/301/299/891
,
639/638/161/891
,
Applied sciences
2014
Flow batteries, in which the electro-active components are held in fluid form external to the battery itself, are attractive as a potential means for regulating the output of intermittent renewable sources of electricity; an aqueous flow battery based on inexpensive commodity chemicals is now reported that also has the virtue of enabling further improvement of battery performance through organic chemical design.
Go with the flow batteries
Flow batteries differ from the conventional type in that the electro-active components of flow batteries are held in fluid form external to the battery itself, enabling such systems to store arbitrarily large amounts of energy. Flow batteries are therefore attractive as a potential means for regulating the output of intermittent sources of electricity such as wind or solar power. But an important limitation of most such systems is the abundance and cost of the electro-active materials. To overcome this limitation, Brian Huskinson and colleagues have developed an aqueous flow battery on the basis of inexpensive, non-metallic commodity chemicals, with the added advantage of enabling the tuning of key battery properties through chemical design.
As the fraction of electricity generation from intermittent renewable sources—such as solar or wind—grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output
1
,
2
. In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form
3
,
4
,
5
. Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious-metal electrocatalysts
6
,
7
. Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br
2
/Br
−
redox couple, yields a peak galvanic power density exceeding 0.6 W cm
−2
at 1.3 A cm
−2
. Cycling of this quinone–bromide flow battery showed >99 per cent storage capacity retention per cycle. The organic anthraquinone species can be synthesized from inexpensive commodity chemicals
8
. This organic approach permits tuning of important properties such as the reduction potential and solubility by adding functional groups: for example, we demonstrate that the addition of two hydroxy groups to AQDS increases the open circuit potential of the cell by 11% and we describe a pathway for further increases in cell voltage. The use of π-aromatic redox-active organic molecules instead of redox-active metals represents a new and promising direction for realizing massive electrical energy storage at greatly reduced cost.
Journal Article
Low energy carbon capture via electrochemically induced pH swing with electrochemical rebalancing
2022
We demonstrate a carbon capture system based on pH swing cycles driven through proton-coupled electron transfer of sodium (3,3′-(phenazine-2,3-diylbis(oxy))bis(propane-1-sulfonate)) (DSPZ) molecules. Electrochemical reduction of DSPZ causes an increase of hydroxide concentration, which absorbs CO
2
; subsequent electrochemical oxidation of the reduced DSPZ consumes the hydroxide, causing CO
2
outgassing. The measured electrical work of separating CO
2
from a binary mixture with N
2
, at CO
2
inlet partial pressures ranging from 0.1 to 0.5 bar, and releasing to a pure CO
2
exit stream at 1.0 bar, was measured for electrical current densities of 20–150 mA cm
−2
. The work for separating CO
2
from a 0.1 bar inlet and concentrating into a 1 bar exit is 61.3 kJ mol
CO2
−1
at a current density of 20 mA cm
−2
. Depending on the initial composition of the electrolyte, the molar cycle work for capture from 0.4 mbar extrapolates to 121–237 kJ mol
CO2
−1
at 20 mA cm
−2
. We also introduce an electrochemical rebalancing method that extends cell lifetime by recovering the initial electrolyte composition after it is perturbed by side reactions. We discuss the implications of these results for future low-energy electrochemical carbon capture devices.
This work demonstrates a safe and scalable electrochemical CO
2
separation method that allows promisingly low (62 kJ/mol
CO2
) energetic cost at a high current density, and it can be used for direct air capture when a suitable molecule is used.
Journal Article
Moonrise timing is key for synchronized spawning in coral Dipsastraea speciosa
by
Mulla, Aziz J.
,
Lin, Che-Hung
,
Nozawa, Yoko
in
Animals
,
Anthozoa - physiology
,
Biological Sciences
2021
Synchronized mass coral spawning typically occurs several days after a full moon once a year. It is expected that spawning day is determined by corals sensing environmental change regulated by the lunar cycle (i.e., tide or moonlight); however, the exact regulatory mechanism remains unknown. Here, we demonstrate how moonlight influences the spawning process of coral, Dipsastraea speciosa. When corals in the field were shaded 1 and 3 d before the full moon or 1 d after the full moon, spawning always occurred 5 d after shading commenced. These results suggest moonlight suppresses spawning: a hypothesis supported by laboratory experiments in which we monitored the effects of experimental moonlight (night-light) on spawning day. Different night-light treatments in the laboratory showed that the presence of a dark period between day-light and night-light conditions eliminates the suppressive effect of night-light on spawning. In nature, moonrise gets progressively later during the course of the lunar cycle, shifting to after sunset following the day of the full moon. Our results indicate that this period of darkness between sunset and moonrise triggers synchronized mass spawning of D. speciosa in nature.
Journal Article
Alkaline quinone flow battery
2015
Storage of photovoltaic and wind electricity in batteries could solve the mismatch problem between the intermittent supply of these renewable resources and variable demand. Flow batteries permit more economical long-duration discharge than solid-electrode batteries by using liquid electrolytes stored outside of the battery. We report an alkaline flow battery based on redox-active organic molecules that are composed entirely of Earth-abundant elements and are nontoxic, nonflammable, and safe for use in residential and commercial environments. The battery operates efficiently with high power density near room temperature. These results demonstrate the stability and performance of redox-active organic molecules in alkaline flow batteries, potentially enabling cost-effective stationary storage of renewable energy.
Journal Article
In situ electrochemical recomposition of decomposed redox-active species in aqueous organic flow batteries
2022
Aqueous organic redox flow batteries offer a safe and potentially inexpensive solution to the problem of storing massive amounts of electricity produced from intermittent renewables. However, molecular decomposition represents a major barrier to commercialization—and although structural modifications can improve stability, it comes at the expense of synthetic cost and molecular weight. Now, utilizing 2,6-dihydroxy-anthraquinone (DHAQ) without further structural modification, we demonstrate that the regeneration of the original molecule after decomposition represents a viable route to achieve low-cost, long-lifetime aqueous organic redox flow batteries. We used in situ (online) NMR and electron paramagnetic resonance, and complementary electrochemical analyses to show that the decomposition compound 2,6-dihydroxy-anthrone (DHA) and its tautomer, 2,6-dihydroxy-anthranol (DHAL) can be recomposed to DHAQ electrochemically through two steps: oxidation of DHA(L)
2−
to the dimer (DHA)
2
4−
by one-electron transfer followed by oxidation of (DHA)
2
4−
to DHAQ
2−
by three-electron transfer per DHAQ molecule. This electrochemical regeneration process also rejuvenates the positive electrolyte—rebalancing the states of charge of both electrolytes without introducing extra ions.
Aqueous organic redox flow batteries offer a safe and inexpensive solution to the problem of storing electricity produced from intermittent renewables. However, decomposition of the redox-active organic molecules that they rely on limits their lifetimes, preventing commercialization. Now it has been shown that these redox molecules can be electro-recomposed in situ, rejuvenating their function.
Journal Article
Long-term cardiovascular safety of febuxostat compared with allopurinol in patients with gout (FAST): a multicentre, prospective, randomised, open-label, non-inferiority trial
by
Wetherall, K.
,
Murphy, D.J.
,
Pigazzani, F.
in
Aged
,
Allopurinol
,
Allopurinol - administration & dosage
2020
Febuxostat and allopurinol are urate-lowering therapies used to treat patients with gout. Following concerns about the cardiovascular safety of febuxostat, the European Medicines Agency recommended a post-licensing study assessing the cardiovascular safety of febuxostat compared with allopurinol.
We did a prospective, randomised, open-label, blinded-endpoint, non-inferiority trial of febuxostat versus allopurinol in patients with gout in the UK, Denmark, and Sweden. Eligible patients were 60 years or older, already receiving allopurinol, and had at least one additional cardiovascular risk factor. Those who had myocardial infarction or stroke in the previous 6 months or who had severe congestive heart failure or severe renal impairment were excluded. After a lead-in phase in which allopurinol dose was optimised towards achieving a serum urate concentration of less than 0·357 mmol/L (<6 mg/dL), patients were randomly assigned (1:1, with stratification according to previous cardiovascular events) to continue allopurinol (at the optimised dose) or start febuxostat at 80 mg/day, increasing to 120 mg/day if necessary to achieve the target serum urate concentration. The primary outcome was a composite of hospitalisation for non-fatal myocardial infarction or biomarker-positive acute coronary syndrome; non-fatal stroke; or cardiovascular death. The hazard ratio (HR) for febuxostat versus allopurinol in a Cox proportional hazards model (adjusted for the stratification variable and country) was assessed for non-inferiority (HR limit 1·3) in an on-treatment analysis. This study is registered with the EU Clinical Trials Register (EudraCT 2011-001883-23) and ISRCTN (ISRCTN72443728) and is now closed.
From Dec 20, 2011, to Jan 26, 2018, 6128 patients (mean age 71·0 years [SD 6·4], 5225 [85·3%] men, 903 [14·7%] women, 2046 [33·4%] with previous cardiovascular disease) were enrolled and randomly allocated to receive allopurinol (n=3065) or febuxostat (n=3063). By the study end date (Dec 31, 2019), 189 (6·2%) patients in the febuxostat group and 169 (5·5%) in the allopurinol group withdrew from all follow-up. Median follow-up time was 1467 days (IQR 1029–2052) and median on-treatment follow-up was 1324 days (IQR 870–1919). For incidence of the primary endpoint, on-treatment, febuxostat (172 patients [1·72 events per 100 patient-years]) was non-inferior to allopurinol (241 patients [2·05 events per 100 patient-years]; adjusted HR 0·85 [95% CI 0·70–1·03], p<0·0001). In the febuxostat group, 222 (7·2%) of 3063 patients died and 1720 (57·3%) of 3001 in the safety analysis set had at least one serious adverse event (with 23 events in 19 [0·6%] patients related to treatment). In the allopurinol group, 263 (8·6%) of 3065 patients died and 1812 (59·4%) of 3050 had one or more serious adverse events (with five events in five [0·2%] patients related to treatment). Randomised therapy was discontinued in 973 (32·4%) patients in the febuxostat group and 503 (16·5%) patients in the allopurinol group.
Febuxostat is non-inferior to allopurinol therapy with respect to the primary cardiovascular endpoint, and its long-term use is not associated with an increased risk of death or serious adverse events compared with allopurinol.
Menarini, Ipsen, and Teijin Pharma Ltd.
Journal Article
Room-temperature sub-band gap optoelectronic response of hyperdoped silicon
by
Sullivan, Joseph T.
,
Persans, Peter D.
,
Winkler, Mark T.
in
140/125
,
639/301/930
,
639/624/1075/401
2014
Room-temperature infrared sub-band gap photoresponse in silicon is of interest for telecommunications, imaging and solid-state energy conversion. Attempts to induce infrared response in silicon largely centred on combining the modification of its electronic structure via controlled defect formation (for example, vacancies and dislocations) with waveguide coupling, or integration with foreign materials. Impurity-mediated sub-band gap photoresponse in silicon is an alternative to these methods but it has only been studied at low temperature. Here we demonstrate impurity-mediated room-temperature sub-band gap photoresponse in single-crystal silicon-based planar photodiodes. A rapid and repeatable laser-based hyperdoping method incorporates supersaturated gold dopant concentrations on the order of 10
20
cm
−3
into a single-crystal surface layer ~150 nm thin. We demonstrate room-temperature silicon spectral response extending to wavelengths as long as 2,200 nm, with response increasing monotonically with supersaturated gold dopant concentration. This hyperdoping approach offers a possible path to tunable, broadband infrared imaging using silicon at room temperature.
Extending the optical response of silicon below the band gap towards infrared wavelengths is of interest for applications such as imaging. Here, Mailoa
et al
. achieve room-temperature infrared photoresponse from silicon doped with supersaturated concentrations of gold impurities.
Journal Article
Photo-movement of coral larvae influences vertical positioning in the ocean
2021
Behaviour can have profound consequences for the dispersal potential of an organism. In the marine environment, larvae rely heavily on oceanic currents to migrate from one area to another. As oceanic currents are faster in the shallows, the vertical positioning of larvae during dispersal is a key factor regulating the distance individuals can travel. Up until now, the vertical positioning of coral larvae has been largely explained by buoyancy, as well as changes in physical and chemical cues. However, here we show that in larvae of coral Pocillopora verrucosa, vertical positioning is influenced by photo-movement. We examined the reaction to light of five coral species in the laboratory and found that only larvae of P. verrucosa, but not other species, displayed a positive photo-response (i.e. an accumulation of larvae close to the light source). This reaction was observed irrespective to the orientation of light from the top, bottom or side. In the field, P. verrucosa larvae accumulated in the top halves of transparent chambers at all depths (1, 7, 15 m), whereas such behaviour failed to occur in dark chambers. Our results demonstrate that light can play an important role for coral larvae to regulate vertical positioning during dispersal and provides a hypothesis that positive photo-movement might allow larvae to disperse further and contribute to the wide geographical distribution of P. verrucosa in the Indo-Pacific.
Journal Article
Film growth mechanisms in pulsed laser deposition
by
Aziz, Michael J.
in
Characterization and Evaluation of Materials
,
Computer simulation
,
Condensed Matter Physics
2008
This paper reviews our recent studies of the fundamentals of growth morphology evolution in Pulsed Laser Deposition in two prototypical growth modes: metal-on-insulator island growth and semiconductor homoepitaxy. By comparing morphology evolution for pulsed laser deposition and thermal deposition in the same dual-use chamber under identical thermal, background, and surface preparation conditions, and varying the kinetic energy by varying the laser fluence or using an inert background gas, we have isolated the effect of kinetic energy from that of flux pulsing in determining the differences between morphology evolution in these growth methods. In each growth mode analytical growth models and Kinetic Monte Carlo simulations for thermal deposition, modified to include kinetic energy effects, are successful at explaining much of what we observe experimentally.
Journal Article
Evolution of nanoporosity in dealloying
by
Sieradzki, Karl
,
Dimitrov, Nikolay
,
Erlebacher, Jonah
in
Alloys
,
Applied sciences
,
Biomaterials
2001
Dealloying is a common corrosion process during which an alloy is ‘parted’ by the selective dissolution of the most electrochemically active of its elements. This process results in the formation of a nanoporous sponge composed almost entirely of the more noble alloy constituents
1
. Although considerable attention has been devoted to the morphological aspects of the dealloying process, its underlying physical mechanism has remained unclear
2
. Here we propose a continuum model that is fully consistent with experiments and theoretical simulations of alloy dissolution, and demonstrate that nanoporosity in metals is due to an intrinsic dynamical pattern formation process. That is, pores form because the more noble atoms are chemically driven to aggregate into two-dimensional clusters by a phase separation process (spinodal decomposition) at the solid–electrolyte interface, and the surface area continuously increases owing to etching. Together, these processes evolve porosity with a characteristic length scale predicted by our continuum model. We expect that chemically tailored nanoporous gold made by dealloying Ag-Au should be suitable for sensor applications, particularly in a biomaterials context.
Journal Article