E01-JEM ARM 200CF
I20-EDE-Energy Dispersive EXAFS (EDE)
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Jesus
Barrio
,
Angus
Pedersen
,
Jingyu
Feng
,
Saurav Ch.
Sarma
,
Mengnan
Wang
,
Alain Y.
Li
,
Hossein
Yadegari
,
Hui
Luo
,
Mary P.
Ryan
,
Maria-Magdalena
Titirici
,
Ifan E. L.
Stephens
Diamond Proposal Number(s):
[28663, 28698]
Open Access
Abstract: Single-atom catalysts, in particular the Fe–N–C family of materials, have emerged as a promising alternative to platinum group metals in fuel cells as catalysts for the oxygen reduction reaction. Numerous theoretical studies have suggested that dual atom catalysts can appreciably accelerate catalytic reactions; nevertheless, the synthesis of these materials is highly challenging owing to metal atom clustering and aggregation into nanoparticles during high temperature synthesis treatment. In this work, dual metal atom catalysts are prepared by controlled post synthetic metal-coordination in a C2N-like material. The configuration of the active sites was confirmed by means of X-ray adsorption spectroscopy and scanning transmission electron microscopy. During oxygen reduction, the catalyst exhibited an activity of 2.4 ± 0.3 A gcarbon−1 at 0.8 V versus a reversible hydrogen electrode in acidic media, comparable to the most active in the literature. This work provides a novel approach for the targeted synthesis of catalysts containing dual metal sites in electrocatalysis.
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Feb 2022
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B18-Core EXAFS
I22-Small angle scattering & Diffraction
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Jingyu
Feng
,
Rongsheng
Cai
,
Emanuele
Magliocca
,
Hui
Luo
,
Luke
Higgins
,
Giulio L. Fumagalli
Romario
,
Xiaoqiang
Liang
,
Angus
Pedersen
,
Zhen
Xu
,
Zhenyu
Guo
,
Arun
Periasamy
,
Dan
Brett
,
Thomas S.
Miller
,
Sarah J.
Haigh
,
Bhoopesh
Mishra
,
Maria-Magdalena
Titirici
Diamond Proposal Number(s):
[26201, 27900]
Open Access
Abstract: Atomically dispersed transition metal-nitrogen-carbon catalysts are emerging as low-cost electrocatalysts for the oxygen reduction reaction in fuel cells. However, a cost-effective and scalable synthesis strategy for these catalysts is still required, as well as a greater understanding of their mechanisms. Herein, iron, nitrogen co-doped carbon spheres (Fe@NCS) have been prepared via hydrothermal carbonization and high-temperature post carbonization. It is determined that FeN4 is the main form of iron existing in the obtained Fe@NCS. Two different precursors containing Fe2+ and Fe3+ are compared. Both chemical and structural differences have been observed in catalysts starting from Fe2+ and Fe3+ precursors. Fe2+@NCS-A (starting with Fe2+ precursor) shows better catalytic activity for the oxygen reduction reaction. This catalyst is studied in an anion exchange membrane fuel cell. The high open-circuit voltage demonstrates the potential approach for developing high-performance, low-cost fuel cell catalysts.
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Aug 2021
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I15-1-X-ray Pair Distribution Function (XPDF)
I15-Extreme Conditions
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Diamond Proposal Number(s):
[17785, 13681]
Abstract: Hard carbons are the leading candidate anode materials for sodium-ion batteries. However, the sodium-insertion mechanisms remain under debate. Here, employing a novel analysis of operando and ex situ pair distribution function (PDF) analysis of total scattering data, supplemented by information on the local electronic structure provided by operando 23Na solid-state NMR, we identify the local atomic environments of sodium stored within hard carbon and provide a revised mechanism for sodium storage. The local structure of carbons is well-described by bilayers of curved graphene fragments, with fragment size increasing, and curvature decreasing with increasing pyrolysis temperature. A correlation is observed between the higher-voltage (slope) capacity and the defect concentration inferred from the size and curvature of the fragments. Meanwhile, a larger lower-voltage (plateau) capacity is observed in samples modeled by larger fragment sizes. Operando PDF data on two commercially relevant hard carbons reveal changes at higher-voltages consistent with sodium ions stored close to defective areas of the carbon, with electrons localized in the antibonding π*-orbitals of the carbon. Metallic sodium clusters approximately 13–15 Å in diameter are formed in both carbons at lower voltages, implying that, for these carbons, the lower-voltage capacity is determined by the number of regions suitable for sodium cluster formation, rather than by having microstructures that allow larger clusters to form. Our results reveal that local atomic structure has a definitive role in determining storage capacity, and therefore the effect of synthetic conditions on both the local atomic structure and the microstructure should be considered when engineering hard carbons.
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Aug 2021
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Nuria
Tapia-Ruiz
,
A. Robert
Armstrong
,
Hande
Alptekin
,
Marco A.
Amores
,
Heather
Au
,
Jerry
Barker
,
Rebecca
Boston
,
William R
Brant
,
Jake M.
Brittain
,
Yue
Chen
,
Manish
Chhowalla
,
Yong-Seok
Choi
,
Sara I. R.
Costa
,
Maria
Crespo Ribadeneyra
,
Serena A
Cussen
,
Edmund J.
Cussen
,
William I. F.
David
,
Aamod V
Desai
,
Stewart A. M.
Dickson
,
Emmanuel I.
Eweka
,
Juan D.
Forero-Saboya
,
Clare
Grey
,
John M.
Griffin
,
Peter
Gross
,
Xiao
Hua
,
John T. S.
Irvine
,
Patrik
Johansson
,
Martin O.
Jones
,
Martin
Karlsmo
,
Emma
Kendrick
,
Eunjeong
Kim
,
Oleg V
Kolosov
,
Zhuangnan
Li
,
Stijn F L
Mertens
,
Ronnie
Mogensen
,
Laure
Monconduit
,
Russell E
Morris
,
Andrew J.
Naylor
,
Shahin
Nikman
,
Christopher A
O’keefe
,
Darren M. C.
Ould
,
Robert G.
Palgrave
,
Philippe
Poizot
,
Alexandre
Ponrouch
,
Stéven
Renault
,
Emily M.
Reynolds
,
Ashish
Rudola
,
Ruth
Sayers
,
David O.
Scanlon
,
S.
Sen
,
Valerie R.
Seymour
,
Begoña
Silván
,
Moulay Tahar
Sougrati
,
Lorenzo
Stievano
,
Grant S.
Stone
,
Chris I.
Thomas
,
Maria-Magdalena
Titirici
,
Jincheng
Tong
,
Thomas J.
Wood
,
Dominic S
Wright
,
Reza
Younesi
Open Access
Abstract: Increasing concerns regarding the sustainability of lithium sources, due to their limited availability and consequent expected price increase, have raised awareness of the importance of developing alternative energy-storage candidates that can sustain the ever-growing energy demand. Furthermore, limitations on the availability of the transition metals used in the manufacturing of cathode materials, together with questionable mining practices, are driving development towards more sustainable elements. Given the uniformly high abundance and cost-effectiveness of sodium, as well as its very suitable redox potential (close to that of lithium), sodium-ion battery technology offers tremendous potential to be a counterpart to lithium-ion batteries (LIBs) in different application scenarios, such as stationary energy storage and low-cost vehicles. This potential is reflected by the major investments that are being made by industry in a wide variety of markets and in diverse material combinations. Despite the associated advantages of being a drop-in replacement for LIBs, there are remarkable differences in the physicochemical properties between sodium and lithium that give rise to different behaviours, for example, different coordination preferences in compounds, desolvation energies, or solubility of the solid–electrolyte interphase inorganic salt components. This demands a more detailed study of the underlying physical and chemical processes occurring in sodium-ion batteries and allows great scope for groundbreaking advances in the field, from lab-scale to scale-up. This roadmap provides an extensive review by experts in academia and industry of the current state of the art in 2021 and the different research directions and strategies currently underway to improve the performance of sodium-ion batteries. The aim is to provide an opinion with respect to the current challenges and opportunities, from the fundamental properties to the practical applications of this technology.
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Jul 2021
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I13-2-Diamond Manchester Imaging
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Diamond Proposal Number(s):
[21587]
Open Access
Abstract: Accurate modelling of particle shrinkage during biomass pyrolysis is key to the production of biochars with specific morphologies. Such biochars represent sustainable solutions to a variety of adsorption-dependent environmental remediation challenges. Modelling of particle shrinkage during biomass pyrolysis has heretofore been based solely on theory and ex-situ experimental data. Here we present the first in-situ phase-contrast X-ray imaging study of biomass pyrolysis. A novel reactor was developed to enable operando synchrotron radiography of fixed beds of pyrolysing biomass. Almond shell particles experienced more bulk shrinkage and less change in porosity than did walnut shell particles during pyrolysis, despite their similar composition. Alkaline pretreatment was found to reduce this difference in feedstock behaviour. Ex-situ synchrotron X-ray microtomography was performed to study the effects of pyrolysis on pore morphology. Pyrolysis led to a redistribution of pores away from particle surfaces, meaning newly formed surface area may be less accessible to adsorbates.
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Jan 2021
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E01-JEM ARM 200CF
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Qian
Guo
,
Hui
Luo
,
Jifang
Zhang
,
Qiushi
Ruan
,
Arun
Prakash Periasamy
,
Yuanxing
Fang
,
Zailai
Xie
,
Xuanhua
Li
,
Xinchen
Wang
,
Junwang
Tang
,
Joe
Briscoe
,
Magdalena
Titirici
,
Ana Belen
Jorge
Diamond Proposal Number(s):
[22447]
Open Access
Abstract: Hematite is a promising candidate as photoanode for solar-driven water splitting, with a theoretically predicted maximum solar-to-hydrogen conversion efficiency of ∼16%. However, the interfacial charge transfer and recombination greatly limits its activity for photoelectrochemical water splitting. Carbon dots exhibit great potential in photoelectrochemical water splitting for solar to hydrogen conversion as photosensitisers and co-catalysts. Here we developed a novel carbon underlayer from low-cost and environmental-friendly carbon dots through a facile hydrothermal process, introduced between the fluorine-doped tin oxide conducting substrate and hematite photoanodes. This led to a remarkable enhancement in the photocurrent density. Owing to the triple functional role of carbon dots underlayer in improving the interfacial properties of FTO/hematite and providing carbon source for the overlayer as well as the change in the iron oxidation state, the bulk and interfacial charge transfer dynamics of hematite are significantly enhanced, and consequently led to a remarkable enhancement in the photocurrent density. The results revealed a substantial improvement in the charge transfer rate, yielding a charge transfer efficiency of up to 80% at 1.25 V vs. RHE. In addition, a significant enhancement in the lifetime of photogenerated electrons and an increased carrier density were observed for the hematite photoanodes modified with a carbon underlayer, confirming that the use of sustainable carbon nanomaterials is an effective strategy to boost the photoelectrochemical performance of semiconductors for energy conversion.
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Sep 2020
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B18-Core EXAFS
E01-JEM ARM 200CF
E02-JEM ARM 300CF
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Hui
Luo
,
Ying
Liu
,
Stoichko D.
Dimitrov
,
Ludmilla
Steier
,
Shaohui
Guo
,
Xuanhua
Li
,
Jingyu
Feng
,
Fei
Xie
,
Yuanxing
Fang
,
Andrei
Sapelkin
,
Xinchen
Wang
,
Maria-Magdalena
Titirici
Diamond Proposal Number(s):
[22447, 20116]
Abstract: Single-atom catalysis has become the most active new frontier in energy conversion applications due to its remarkable catalytic activity and low material consumption. However, the issue of atom aggregation during the synthesis process or catalytic reaction must be overcome. In this work, we have developed a one-step photo-deposition process to fabricate Pt single-atom catalysts (SACs) on nitrogen doped carbon dots (NCDs). The Pt–NCDs were then hybridized with TiO2 to achieve high hydrogen generation activity and to understand the fundamentals at the Pt/NCD/TiO2 interface. The synergistic effect of Pt SAC and NCDs with maximized atomic efficiency of Pt and improved charge transfer capability provides a new strategy to rationally design a multi-scale photocatalyst structure to achieve high H2 evolution efficiency. The facile synthesis process also holds great potential for various applications such as electrocatalysis, heterogeneous catalysis and drug delivery, providing a promising way to reduce the high cost of noble metals.
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Jul 2020
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E01-JEM ARM 200CF
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Hui
Luo
,
Stoichko D.
Dimitrov
,
Matyas
Daboczi
,
Ji-Seon
Kim
,
Qian
Guo
,
Yuanxing
Fang
,
Marc-Antoine
Stoeckel
,
Paolo
Samorì
,
Oliver
Fenwick
,
Ana Belen
Jorge Sobrido
,
Xinchen
Wang
,
Maria-Magdalena
Titirici
Diamond Proposal Number(s):
[22447]
Abstract: Carbon dots on photoactive semiconductor nanomaterials have represented an effective strategy for enhancing their photoelectrochemical (PEC) activity. By carefully designing and manipulating carbon dots/support composite, a high photocurrent could be obtained. Currently, there is not much fundamental understanding of how the interaction between such materials can facilitate the reaction process. This hinders the wide applicability in PEC devices. To address this need of improving the fundamental understanding of carbon dots/semiconductor nanocomposite, we have taken the TiO2 case as a model semiconductor system with nitrogen-doped carbon dots (NCDs). We present here with in-depth investigation of the structural hybridization and energy transitions in the NCDs/TiO2 photoelectrode via high-resolution scanning transmission microscopy (HR-STEM), electron energy loss spectroscopy (EELS), UV-Vis absorption, electrochemical impedance spectroscopy (EIS), Mott-Schottky (M-S), time-correlated single photon counting (TCSPC) and ultra-violet photoelectron spectroscopy (UPS), which shed some light on the charge transfer process at the carbon dots and TiO2 interface. We show that N doping in carbon dots can effectively prolong the carrier lifetime, and the hybridisation of NCDs and TiO2 is able not only to extend TiO2 light response into the visible range but also to form heterojunction at the NCDs/TiO2 interface with properly aligned band structure that allows a spatial separation of the charges. This work is arguably the first to report the direct probing of the band positions of carbon dots-TiO2 nanoparticle composite in a PEC system for understanding the energy transfer mechanism, demonstrating the favourable role of NCDs in the photocurrent response of TiO2 for water oxidation process. This study reveals the importance of combining structural, photophysical and electrochemical experiments to develop a comprehensive understanding of the charge injection/electronic communication between the carbon dots and their current collectors or catalyst supports.
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Mar 2020
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E01-JEM ARM 200CF
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Hui
Luo
,
Nikolaos
Papaioannou
,
Enrico
Salvadori
,
Maxie
Roessler
,
Gereon
Ploenes
,
Ernst R. H.
Van Eck
,
Liviu
Tanase
,
Jingyu
Feng
,
Yiwei
Sun
,
Yan
Yang
,
Mohsen
Danaie
,
Ana
Jorge Sobrido
,
Andrei
Sapelkin
,
James
Durrant
,
Stoichko D.
Dimitrov
,
Maria-Magdalena
Titirici
Diamond Proposal Number(s):
[17587]
Abstract: As a new class of sustainable carbon material, the term “carbon dots” represents an “umbrella term” as there are many types of materials included. We employ a broad range of techniques to develop understanding on hydrothermally synthesized carbon dots and show how fine tuning the structural features using simple reduction/oxidation reactions can drastically affect their excited state properties. Structural and spectroscopic studies found that photoluminescence originates from direct excitation of localized fluorophores involving oxygen functional groups, while the excitation at graphene‐like features leads to ultrafast phonon‐assisted relaxation and largely quenches the fluorescent quantum yields. This is arguably the first to identify the dynamics of photoluminescence including Stokes’ shift formation, allowing us to fully resolve the relaxation pathways in these carbon dots. The comprehensive investigation sheds light on how understanding the excited state relaxation processes in different carbon structure is crucial for tuning the optical properties for any potential commercial applications.
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Aug 2019
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