Imperial College London

Professor Jason Riley

Faculty of EngineeringDepartment of Materials

Vice-Dean (Education) for the Faculty of Engineering
 
 
 
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Contact

 

+44 (0)20 7594 6751jason.riley

 
 
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Location

 

B3.37Bessemer BuildingSouth Kensington Campus

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Summary

 

Publications

Publication Type
Year
to

113 results found

Zhang H, Diao J, Liu Y, Zhao H, Ng BKY, Ding Z, Guo Z, Li H, Jia J, Yu C, Xie F, Henkelman G, Titirici M-M, Robertson J, Nellist P, Duan C, Guo Y, Riley DJ, Qiu Jet al., 2023, In-situ grown Cu dendrites plasmonically enhance electrocatalytic hydrogen evolution on facet-engineered Cu₂O, Advanced Materials, Vol: 35, ISSN: 0935-9648

Electrocatalytic hydrogen evolution reaction (HER) is widely regarded as one of the most efficient and sustainable strategies for hydrogen production. Up to now, most electrocatalysis research related to HER mainly focuses on stand-alone electrocatalysis and fails to pay attention to the integration of other driving forces such as light. Herein, Cu2 O nanostructures with different exposed crystal facets were synthesized by wet chemical methods for electrocatalytic HER, and it was found that the octahedral Cu2 O nanostructures with exposed crystal planes of (111) (O-Cu2 O) had the best hydrogen evolution performance. Density functional theory (DFT) calculations found that the better HER performance on Cu2 O (111) facets was attributed to the lower energy barrier in the Heyrovsky step. Operando Raman spectroscopy and ex-situ characterization techniques showed that Cu2 O was reduced during HER, in which Cu dendrites were grown on the surface of the Cu2 O nanostructures, resulting in the better HER performance of O-Cu2 O after HER (O-Cu2 O-A) compared with that of the as-prepared O-Cu2 O. DFT calculations indicated that the charge transfer at the Cu2 O/Cu interface enhanced its surface electron concentration. Under illumination, the onset potential of O-Cu2 O-A is ca. 52 mV positive than that of O-Cu2 O, which is induced by the plasmon-activated electrochemical system consisting of Cu2 O and the in-situ generated Cu dendrites. Incident photon-to-current efficiency (IPCE) measurements, ultraviolet-visible (UV-Vis) spectroscopy and X-ray photoelectron spectroscopy (XPS) demonstrate the hot electron injection (HEI) from Cu dendrites to Cu2 O. Ab initio nonadiabatic molecular dynamics (NAMD) simulations revealed that the transfer of photogenerated electrons (27 fs) from Cu dendrites to Cu2 O nanostructures is faster than electron relaxation (170 fs), enhancing its surface plasmons activity, and the HEI of Cu dendrites increases the charge density of Cu2 O. These make t

Journal article

Ji C, Xu J, Jiang Q, Kerherve G, Zhou H, li X, Tang S, Sharma P, Riley DJ, Xie Fet al., 2023, Significantly boosted photoelectrochemical water splitting performance by plasmonic enhanced Hematite@MOF composite photoelectrodes, Materials Today Advances, Vol: 18, Pages: 1-13, ISSN: 2590-0498

Hematite as a catalyst for photoelectrochemical water splitting offers huge potential, due to its high chemical stability, great abundance, and low cost. However, the low water oxidation kinetics and poor charge transportation have hindered progress towards the manufacture of practical water splitting devices. To tackle these problems, a visible light responsive metal-organic framework (MOF) polyhedral zeolitic imidazolate (ZIF-67), and optimised plasmonic Ag nanorods were incorporated into hematite nanostructures to form a three-component heterojunction photoelectrode. The designed photoanode showed dramatically improved light harvesting in the visible range and enhanced charge transport. A mechanistic investigation allowed the deconvolution of the enhanced performance pathways. First, the Hematite@ZIF-67 core-shell p-n junction enables facile charge carrier transfer between ZIF-67 and hematite. In addition, ZIF-67 also provides active sites for water oxidation and boosts surface oxygen evolution reaction (OER) kinetics. Guided by finite-difference time-domain (FDTD) modelling, Ag nanorods with optimised aspect ratio were incorporated between ZIF-67 and hematite. The Ag nanorods facilitate broadband light absorption and surface charge injection, induced by near-field excitation enhancement and plasmonic resonance energy transfer (PRET) pathways. The design and addition of ZIF-67 and Ag nanorods result in superior performance for a hematite-based photoanode for photoelectrochemical (PEC) water oxidation.

Journal article

Tian T, Xu J, Abdolazizi A, Ji C, Hou J, Riley DJ, Yan C, Ryan MP, Xie F, Petit Cet al., 2023, Occurrence, geochemical characteristics, enrichment, and ecological risks of rare earth elements in sediments of "the Yellow river- Estuary- bay" system*, MATERIALS TODAY NANO, Vol: 21, ISSN: 2588-8420

Journal article

Zhang H, Diao J, Ouyang M, Yadegari H, Mao M, Wang M, Henkelman G, Xie F, Riley DJet al., 2023, Heterostructured core-Shell Ni-Co@Fe-Co nanoboxes of prussian blue analogues for efficient electrocatalytic hydrogen evolution from alkaline seawater., ACS Catalysis, Vol: 13, Pages: 1349-1358, ISSN: 2155-5435

The rational construction of efficient and low-cost electrocatalysts for the hydrogen evolution reaction (HER) is critical to seawater electrolysis. Herein, trimetallic heterostructured core-shell nanoboxes based on Prussian blue analogues (Ni-Co@Fe-Co PBA) were synthesized using an iterative coprecipitation strategy. The same coprecipitation procedure was used for the preparation of the PBA core and shell, with the synthesis of the shell involving chemical etching during the introduction of ferrous ions. Due to its unique structure and composition, the optimized trimetallic Ni-Co@Fe-Co PBA possesses more active interfacial sites and a high specific surface area. As a result, the developed Ni-Co@Fe-Co PBA electrocatalyst exhibits remarkable electrocatalytic HER performance with small overpotentials of 43 and 183 mV to drive a current density of 10 mA cm-2 in alkaline freshwater and simulated seawater, respectively. Operando Raman spectroscopy demonstrates the evolution of Co2+ from Co3+ in the catalyst during HER. Density functional theory simulations reveal that the H*-N adsorption sites lower the barrier energy of the rate-limiting step, and the introduced Fe species improve the electron mobility of Ni-Co@Fe-Co PBA. The charge transfer at the core-shell interface leads to the generation of H* intermediates, thereby enhancing the HER activity. By pairing this HER catalyst (Ni-Co@Fe-Co PBA) with another core-shell PBA OER catalyst (NiCo@A-NiCo-PBA-AA) reported by our group, the fabricated two-electrode electrolyzer was found to achieve high output current densities of 44 and 30 mA cm-2 at a low voltage of 1.6 V in alkaline freshwater and simulated seawater, respectively, exhibiting remarkable durability over a 100 h test.

Journal article

Zhang H, Diao J, Ouyang M, Yadegari H, Mao M, Wang J, Henkelman G, Xie F, Riley DJet al., 2022, Enhancing the performance of Bi2S3 in electrocatalytic and supercapacitor applications by controlling lattice strain, Advanced Functional Materials, Vol: 32, Pages: 1-12, ISSN: 1616-301X

Lattice-strained Bi2S3 with 3D hierarchical structures are prepared through a top-down route by a topotactic transformation. High-resolution transmission electron microscopy and X-ray diffraction (XRD) confirm the lattice spacing is expanded by prolonged sulfuration. Performance studies demonstrate that Bi2S3 with the largest lattice expansion (Bi2S3-9.7%, where 9.7% represents the lattice expansion) exhibits a greater electrocatalytic hydrogen evolution reaction (HER) activity compared to Bi2S3 and Bi2S3-3.2%. Density functional theory calculations reveal the expansion of the lattice spacing reduces the bandwidth and upshifts the band center of the Bi 3d orbits, facilitating electron exchange with the S 2p orbits. The resultant intrinsic electronic configuration exhibits favorable H* adsorption kinetics and a reduced energy barrier for water dissociation in hydrogen evolution. Operando Raman and post-mortem characterizations using XRD and X-ray photoelectron spectroscopy reveal the generation of pseudo-amorphous Bi at the edge of Bi2S3 nanorods of the sample with lattice strain during HER, yielding Bi2S3-9.7%-A. It is worth noting when Bi2S3-9.7%-A is assembled as a positive electrode in an asymmetric supercapacitor, its performance is greatly superior to that of the same device formed using pristine Bi2S3-9.7%. The as-prepared Bi2S3-9.7%-A//activated carbon asymmetric supercapacitor achieves a high specific capacitance of 307.4 F g−1 at 1 A g−1, exhibiting high retention of 84.1% after 10 000 cycles.

Journal article

Zhang H, Geng S, Ouyang M, Yadegari H, Xie F, Riley DJet al., 2022, A self-reconstructed bifunctional electrocatalyst of pseudo-amorphous nickel carbide @ iron oxide network for seawater splitting., Advanced Science, Vol: 9, Pages: 1-15, ISSN: 2198-3844

Here, a sol-gel method is used to prepare a Prussian blue analogue (NiFe-PBA) precursor with a 2D network, which is further annealed to an Fe3 O4 /NiCx composite (NiFe-PBA-gel-cal), inheriting the ultrahigh specific surface area of the parent structure. When the composite is used as both anode and cathode catalyst for overall water splitting, it requires low voltages of 1.57 and 1.66 V to provide a current density of 100 mA cm-2 in alkaline freshwater and simulated seawater, respectively, exhibiting no obvious attenuation over a 50 h test. Operando Raman spectroscopy and X-ray photoelectron spectroscopy indicate that NiOOH2-x active species containing high-valence Ni3+ /Ni4+ are in situ generated from NiCx during the water oxidation. Density functional theory calculations combined with ligand field theory reveal that the role of high valence states of Ni is to trigger the production of localized O 2p electron holes, acting as electrophilic centers for the activation of redox reactions for oxygen evolution reaction. After hydrogen evolution reaction, a series of ex situ and in situ investigations indicate the reduction from Fe3+ to Fe2+ and the evolution of Ni(OH)2 are the origin of the high activity.

Journal article

Zhang H, Li P, Zhou H, Xu J, Jiang Q, Hadden JHL, Wang Y, Wang M, Chen S, Xie F, Riley DJet al., 2022, Unravelling the synergy of oxygen vacancies and gold nanostars in hematite for the electrochemical and photoelectrochemical oxygen evolution reaction, Nano Energy, Vol: 94, Pages: 1-10, ISSN: 2211-2855

The development of hematite-based electrocatalysts (EC) and photoelectrocatalysts (PEC) for oxygen evolution reaction (OER) is highly promising on account of the low-cost and favorable chemical properties. Herein, we report a unique inverse opal framework hematite-based bi-functional catalyst for both EC and PEC water oxidation in alkaline media. Under the combined action of oxygen vacancies (Vo) and gold nanostars (AuNSs) on hematite, the catalyst exhibited excellent activity and stability on both EC and PEC. The composite showed superior electrocatalytic performance for OER with a low overpotential of 281 mV at 10 mA cm−2. Density functional theory (DFT) studies reveal that the coverage of Vo controls the d-band center of surface Fe sites, and the OER activity displays a volcano relationship with the Vo coverage. The addition of gold nanoparticles on the hematite with low Vo coverage improves the adsorption strength of oxygen-containing intermediates to the optimal point and increases the OER activity. Furthermore, the as-prepared photoanode exhibits a ∼3.13 fold increase in current (1.46 mA cm−2) at 1.23 V versus RHE. It is proposed that Vo promotes bulk conductivity and surface catalysis and exhibits reduced activation energy under high light intensity. AuNSs efficiently inhibits the bulk recombination and improves carrier concentration because of the Fermi level equilibration and plasmonic resonance, and the surface catalysis compensates the deterioration of interfacial recombination of carriers induced by Vo, playing a synergistic role.

Journal article

Zhang H, Geng S, Ouyang M, Mao M, Xie F, Riley DJet al., 2022, Using metal cation to control the microstructure of cobalt oxide in energy conversion and storage applications, Small, Vol: 18, Pages: 1-13, ISSN: 1613-6810

Herein, a facile and efficient synthesis of microstructured Co3O4 for both supercapacitor and water-splitting applications is reported. Metal cations (Fe3+, Cu2+) serve as structure-directing agents regulating the structure of Co compounds, which are subsequently annealed to yield Co3O4. Detailed characterizations and density functional theory (DFT) calculations reveal that the in situ Cl-doping introduces oxygen defects and provides abundant electroactive sites, and narrows the bandgap, which enhances the electron excitation of the as-formed Co3O4. The as-prepared Cl-doped Co3O4 hierarchical nanospheres (Cl-Co3O4-h) display a high specific capacitance of 1629 F g−1 at 1 A g−1 as an electrode for supercapacitors, with excellent rate capability and cyclability. The Cl-Co3O4-h//activated carbon (AC) asymmetric supercapacitor (ASC) electrode achieves a specific capacitance of 237 F g−1 at 1 A g−1, with an energy density of 74 Wh kg−1 at a power density of 807 W kg−1 and even maintains 47 Wh kg−1 at the higher-power density of 24.2 kW kg−1. An integrated electrolyzer for water-splitting with Cl-Co3O4-h as both cathode and anode can be driven by Cl-Co3O4-h//AC ASC. The electrolyzer provides a high current density of 35 mA cm–2 at a cell voltage of 1.6 V, with good current density retention over 50 h.

Journal article

Hadden J, Riley DJ, Morgan G, Bouchet Met al., 2021, Mechanism of actuation in nickel hydroxide/oxyhydroxide photoactuators, Advanced Materials Interfaces, Vol: 8, Pages: 1-11, ISSN: 2196-7350

Understanding novel actuating materials which respond to a variety of stimuli is key in the development of micro/nanoscale robotics. In this work, the mechanism of actuation in nickel hydroxide/oxyhydroxide actuators by the intercalation/deintercalation of water is examined. This effect is studied under the stimuli of visible light, photoactuation, and by increased environmental temperature, thermoactuation.The photoactuation has been modelled using a mechanical model, and it has been demonstrated that the experimentally observed intrinsic strain can be achieved with a low deintercalation of water, around 1%. This low level of water exchange is supported by structural changes observed during heating using thin film XRD, as well as ToF-SIMS by isotopic exchange using D2O. These results show the water intercalation hypothesis is both possible and measurable. Future development must take this mechanism into account when designing materials for improved actuation performance.

Journal article

Zhang H, Li P, Chen S, Xie F, Riley DJet al., 2021, Anodic transformation of a core-shell Prussian Blue analogue to a bifunctional electrocatalyst for water splitting, Advanced Functional Materials, Vol: 31, ISSN: 1616-301X

Developing low-cost oxygen evolution reaction (OER) catalysts with high efficiency and understanding the underlying reaction mechanism are critical for electrochemical conversion technologies. Here, an anodized Prussian blue analogue (PBA) containing Ni and Co is reported as a promising OER electrocatalyst in alkaline media. Detailed post-mortem characterizations indicate the transformation from PBA to Ni(OH)2 during the anodic process, with the amorphous shell of the PBA facilitating the transformation by promoting greater structural flexibility. Further study with operando Raman and X-ray photoelectron spectroscopy reveal the increase of anodic potential improves the degree of deprotonation of the transformed core-shell PBA, leading to an increase of Ni valence. Density functional theory calculations suggest that the increase of Ni valence results in a continuous increase in the adsorption strength of oxygen-containing species, exhibiting a volcano relationship against the OER activity. Based on the experiments and calculated results, an OER mechanism for the transformed product is proposed. The fully activated catalyst also works as the cathode and the anode for a water-splitting electrolysis cell with a high output current density of 13.7 mA cm−2 when a cell voltage of 1.6 V applied. No obvious performance attenuation is observed after 40 h of catalysis.

Journal article

Zhang H, Jiang Q, Hadden JHL, Xie F, Riley DJet al., 2021, Pd ion-exchange and ammonia etching of a Prussian blue analogue to produce a high-performance water-splitting catalyst, Advanced Functional Materials, Vol: 31, Pages: 1-15, ISSN: 1616-301X

The authors report an ammonia‐assisted in situ cation‐exchange method for the synthesis of dodecagon N‐doped PdCoNi carbon‐based nanosheets (Pd‐e‐NiCo‐PBA‐C) and explore the catalytic performance. Pd‐e‐NiCo‐PBA‐C exerts extremely low overpotential and Tafel slope for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) both in acidic and alkaline media, only 47 mV, 55 mV dec−1 (pH = 0, HER) and 147 mV, 67 mV dec−1 (pH = 14, HER), and 309 mV, 67 mV dec−1 (pH = 14, OER), outperforming commercial IrO2‐based and Pt‐based catalysts. In addition, after 5000 cycles, the linear sweep voltammetry curve shows a negligible shift, indicating excellent stability performance. To test its overall water‐splitting performance, Pd‐e‐NiCo‐PBA‐C is applied as both cathode and anode materials. A high current density of 33 mA cm−2 at a battery voltage of 1.6 V is obtained, with the catalytic activity maintained at 97.3% after over 50 h. To get a further insight into the superior OER and HER performance, theoretical calculations are carried out, the better performance originates from the affinity difference of Pd and Ni atoms for gas atoms, and the replacement of inert atoms can decrease the binding energy and enhance the electrocatalytic activity.

Journal article

Song W, Stein Scholtis E, sherrel P, deana T, Ngiam J, Lischner J, Fearn S, Bemmer V, Mattevi C, Klein N, Xie F, riley Jet al., 2020, Electronic Structure Influences on the Formation of the Solid Electrolyte Interphase, Energy and Environmental Science, ISSN: 1754-5692

Journal article

Jiang Q, xiangyu X, Riley DJ, Xie Fet al., 2020, Harvesting the lost photon by plasmonic enhanced hematite-upconversion nanocomposite for water splitting, Journal of Chemical Physics, Vol: 153, Pages: 011102-1-011102-6, ISSN: 0021-9606

Converting solar energy to chemical energy in the form of hydrogen via water splitting is one of the promising strategies to solve the global energy crisis. Hematite, a traditional semiconducting oxide photoelectrode, can only absorb UV and visible parts of the solar spectrum, losing 40% infrared energy. In this paper, we report a novel plasmonic enhanced water splitting photoanode based on hematite-lanthanide upconversion nanocomposites to harvest lost photons below the bandgap of hematite. NaYF4:Er, Yb upconversion nanoparticles can upconvert photons from 980 nm to 510 nm–570 nm within the bandgap of hematite. More importantly, a gold nanodisk array with a plasmonic peak centered ∼1000 nm can further boost the photocurrent by 93-fold. It is demonstrated that the excitation process of lanthanide upconversion nanoparticles can be significantly enhanced by plasmonic nanostructures and can thus improve the water oxidation activity via plasmonic enhanced upconversion and hot electron injection, respectively. This new promising strategy will pave the way for plasmonic enhanced lost photon harvesting for applications in solar energy conversion.

Journal article

Hadden JHL, Ryan MP, Riley DJ, 2020, Is nickel hydroxide charging only skin-deep?, ACS Applied Energy Materials, Vol: 3, Pages: 2803-2810, ISSN: 2574-0962

The depth of charging in Ni(OH)2-coated electrodes treated with paraffin wax to remove porosity has been investigated using time-of-flight secondary-ion mass spectrometry after charging and discharging in deuterated solvent at pH 14. The proportion of deuterium uptake was found to be dependent on the number of charge/discharge cycles, showing that the measured deuterium signal was indeed dependent on the electrochemical redox activity of the sample. Sputter craters were characterized using atomic force microscopy to find the sputter rate. This then allowed the maximum depth of charging to be found to be approximately 20 nm. This confirmed a surface “skin” in which charging occurs with the rest of the bulk inactive.

Journal article

Song W, Jiang Q, Xie X, Brookfield A, McInnes EJL, Shearing PR, Brett DJL, Xie F, Riley DJet al., 2019, Synergistic storage of lithium ions in defective anatase/rutile TiO2 for high-rate batteries, Energy Storage Materials, Vol: 22, Pages: 441-449, ISSN: 2405-8297

Fabrication of heterostructured materials is a strategy to boost the charge-transfer kinetics and the performance of high-rate lithium storage. Here, a facile, low-temperature method for the synthesis of high-area TiO2 nanospheres containing both anatase and rutile phases is described. The as-prepared materials contain a high concentration of oxygen vacancies facilitating electron conduction in the anatase phase and theoretical calculations provide evidence of a low energy barrier for Li+ transport in the rutile phase. The synergy between the two phases renders the shared conduction of electrons through anatase and Li+ ions via rutile at high-current rates, leading to the anodes that outperform the alternate TiO2 systems when the combination of capacity at high current densities and cycle stability are considered, displaying a capacity of 95.4 mAh g−1 at 10 A g−1 and a 97.2% retention of capacity over 500 cycles at 1 A g−1.

Journal article

Hadden JHL, Ryan MP, Riley DJ, 2019, Examining the charging behaviour of nickel hydroxide nanomaterials, Electrochemistry Communications, Vol: 101, Pages: 47-51, ISSN: 1388-2481

To investigate the depth of charging at the material surface, batches of nickel hydroxide nanoparticles were hydrothermally synthesised in the range 3–450 nm. Any surfactant added was removed post synthesis using ozone. The capacity per gram (Cs) increased and the capacity per unit area (CA) was constant with decreasing particle size down to 20 nm. Further reduction in particle size resulted in a decrease in both CS and CA, suggesting the Ni(OH)2 is charged to a depth in the order of 10 nm at the charging rate studied. The results obtained have implications in the design of Ni(OH)2 electrodes in charge storage applications.

Journal article

Song W, Liu X, Wu B, Brandon N, Shearing PR, Brett DJL, Xie F, Jason Riley Det al., 2019, Sn@C evolution from yolk-shell to core-shell in carbon nanofibers with suppressed degradation of lithium storage, Energy Storage Materials, Vol: 18, Pages: 229-237, ISSN: 2405-8297

Metallic Sn has high conductivity and high theoretical capacity for lithium storage but it suffers from severe volume change in lithiation/delithiation leading to capacity fade. Yolk-shell and core-shell Sn@C spheres interconnected by carbon nanofibers were synthesized by thermal vapor and thermal melting of electrospun nanofibers to improve the cycling stability. Sn particles in yolk-shell spheres undergo dynamic structure evolution during thermal melting to form core-shell spheres. The core-shell spheres linked along the carbon nanofibers show outstanding performance and are better than the yolk-shell system for lithium storage, with a high capacity retention of 91.8% after 1000 cycles at 1 A g-1. The superior structure of core-shell spheres interconnected by carbon nanofibers has facile electron conductivity and short lithium ion diffusion pathways through the carbon nanofibers and shells, and re-develops Sn@C structures with Sn clusters embedded into carbon matrix during electrochemical cycling, enabling the high performance.

Journal article

Jiang Q, Ji C, Riley DJ, Xie Fet al., 2019, Boosting the efficiency of photoelectrolysis by the addition of non-noble plasmonic metals: Al & Cu, Nanomaterials, Vol: 9, ISSN: 2079-4991

Solar water splitting by semiconductor based photoanodes and photocathodes is one of the most promising strategies to convert solar energy to chemical energy to meet the high demand for energy consumption in modern society. However, the state-of-the-art efficiency is too low to fulfill the demand. To overcome this challenge and thus enable the industrial realization of a solar water splitting device, different approaches have been taken to enhance the overall device efficiency, one of which is the incorporation of plasmonic nanostructures. Photoanodes and photocathodes coupled to the optimized plasmonic nanostructures, matching the absorption wavelength of the semiconductors, can exhibit a significantly increased efficiency. So far, gold and silver have been extensively explored to plasmonically enhance water splitting efficiency, with disadvantages of high cost and low enhancement. Instead, non-noble plasmonic metals such as aluminum and copper, are earth-abundant and low cost. In this article, we review their potentials in photoelectrolysis, towards scalable applications.

Journal article

Riley DJ, Song W, Xie F, Shearing PR, Brett D, Aguadero A, Kangyu Jet al., 2018, Co3O4 hollow nanospheres doped with ZnCo2O4 via thermal vapor mechanism for fast lithium storage., Energy Storage Materials, Vol: 14, Pages: 324-334, ISSN: 2405-8297

Binary metal oxides offer improved anode materials in lithium ion batteries owing to enhanced electrical conductivity but suffer from large volume expansion on lithiation. A novel route to hollow Co3O4 nanospheres doped with ZnCo2O4 is demonstrated that mitigates the expansion issue and shows excellent performance at high current densities. The synthetic route is based on the pyrolysis of binary metal-organic-frameworks (MOFs) with the controlled loss of zinc tuning the micro and nanostructure of the material through a thermal vapor mechanism. The optimal structures, that contain hollow Co3O4 spheres of ca. 50 nm diameter doped with ZnCo2O4, show a specific capacity of 890 mAh g−1 at a current rate of 0.1 A g−1 and show a similar specific capacity at 1 A g−1 after 120 cycles at high current densities. The kinetics of lithiation/delithiation changes from diffusion-controlled to a surface-controlled process by the nanosizing of the particles. The resultant faster ion diffusion and capacitive storage for lithium ions are responsible for the extraordinary high-rate performance of the hollow structures.

Journal article

Ballantyne AD, Hallett JP, Riley DJ, Shah N, Payne DJet al., 2018, Lead acid battery recycling for the twenty-first century, Royal Society Open Science, Vol: 5, Pages: 171368-171368, ISSN: 2054-5703

There is a growing need to develop novel processes to recover lead from end-of-life lead-acid batteries, due to increasing energy costs of pyrometallurgical lead recovery, the resulting CO2 emissions and the catastrophic health implications of lead exposure from lead-to-air emissions. To address these issues, we are developing an iono-metallurgical process, aiming to displace the pyrometallurgical process that has dominated lead production for millennia. The proposed process involves the dissolution of Pb salts into the deep eutectic solvent (DES) Ethaline 200, a liquid formed when a 1 : 2 molar ratio of choline chloride and ethylene glycol are mixed together. Once dissolved, the Pb can be recovered through electrodeposition and the liquid can then be recycled for further Pb recycling. Firstly, DESs are being used to dissolve the lead compounds (PbCO3, PbO, PbO2 and PbSO4) involved and their solubilities measured by inductively coupled plasma optical emission spectrometry (ICP-OES). The resulting Pb2+ species are then reduced and electrodeposited as elemental lead at the cathode of an electrochemical cell; cyclic voltammetry and chronoamperometry are being used to determine the electrodeposition behaviour and mechanism. The electrodeposited films were characterized by scanning electron microscopy (SEM) and X-ray photoelectron spectroscopy (XPS). We discuss the implications and opportunities of such processes.

Journal article

Song W, Brugge R, Theodorou IG, Lim AL, Yang Y, Zhao T, Burgess CH, Johnson ID, Aguadero A, Shearing PR, Brett DJL, Xie F, Riley DJet al., 2017, Enhancing Distorted Metal Organic Framework Derived ZnO as Anode Material for Lithium Storage by the Addition of Ag2S Quantum Dots., ACS Applied Materials and Interfaces, Vol: 9, Pages: 37823-37831, ISSN: 1944-8244

The lithium storage properties of the distorted metal-organic framework (MOF) derived nanosized ZnO@C are significantly improved by the introduction of Ag2S quantum dots (QDs) during the processing of the material. In the thermal treatment, the Ag2S QDs react to produce Ag nanoparticles and ZnS. The metal nanoparticles act to shorten electron pathways and improve the connectivity of the matrix and the partial sulfidation of the ZnO surface improves the cycling stability of the material. The electrochemical properties of ZnO@C, Ag2S QDs treated ZnO@C and the amorphous carbon in ZnO@C have been compared. The small weight ratio of Ag2S QDs to ZnO@C at 1:180 shows the best performance in lithium storage. The exhibited specific capacities are improved and retained remarkably in the cycling at high current rates. At low current densi-ties (200 mA g-1) treatment of ZnO@C with Ag2S QDs results in a 38% increase in the specific capacity.

Journal article

Amdursky N, Wang X, Meredith P, Riley DJ, Payne DJ, Bradley D, Stevens MMet al., 2017, Electron Hopping Across Hemin-Doped Serum Albumin Mats on Centimetre-Length Scales, Advanced Materials, Vol: 29, ISSN: 1521-4095

Exploring long-range electron transport across protein assemblies is a central interest in both the fundamental research of biological processes and the emerging field of bioelectronics. This work examines the use of serum-albumin-based freestanding mats as macroscopic electron mediators in bioelectronic devices. In particular, this study focuses on how doping the protein mat with hemin improves charge-transport. It is demonstrated that doping can increase conductivity 40-fold via electron hopping between adjacent hemin molecules, resulting in the highest measured conductance for a protein-based material yet reported, and transport over centimeter length scales. The use of distance-dependent AC impedance and DC current–voltage measurements allows the contribution from electron hopping between adjacent hemin molecules to be isolated. Because the hemin-doped serum albumin mats have both biocompatibility and fabrication simplicity, they should be applicable to a range of bioelectronic devices of varying sizes, configurations, and applications.

Journal article

Riley DJ, Song W, Lischner, Rocha VG, Qin H, Qi J, Hadden JHL, Mattevi, Xie Fet al., 2017, Tuning the Double Layer of Graphene Oxide through Phosphorus Doping for Enhanced Supercapacitance, ACS Energy Letters, Vol: 2, Pages: 1144-1149, ISSN: 2380-8195

The electrochemical double layer plays a fundamental role in energy storage applications. Control of the distribution of ions in the double layer at the atomistic scale offers routes to enhanced material functionality and device performance. Here we demonstrate how the addition of an element from the third row of the periodic table, phosphorus, to graphene oxide increases the measured capacitance and present density functional theory calculations that relate the enhanced charge storage to structural changes of the electrochemical double layer. Our results point to how rational design of materials at the atomistic scale can lead to improvements in their performance for energy storage.

Journal article

Poll CG, Nelson G, Pickup DM, Chadwick AV, Riley D, Payne DJet al., 2016, Electrochemical recycling of lead from hybrid organic–inorganic perovskites using deep eutectic solvents, Green Chemistry, Vol: 18, Pages: 2946-2955, ISSN: 1463-9262

The emerging field of lead-based hybrid organic–inorganic perovskite (HOIP) photovoltaic devices has attracted a great deal of attention due to their very high conversion efficiencies and straightforward fabrication methods. Unfortunately, a major obstacle to commercialization remains the high toxicity of lead. Whilst to date the focus has been on understanding and improving device performance, there has been no reported effort to develop methods to recover and recycle the lead from these materials. In this work we demonstrate a simple, low-cost and environmentally friendly method of recycling lead from HOIP photovoltaics by dissolution and selective electrodeposition using a deep eutectic solvent. We demonstrate that up to 99.8% of the lead is removed from the solvent. The results presented here provide a viable solution to lead-based HOIP photovoltaic recycling, and also open the possibility for providing an alternative method to conventional smelting in the recovery and recycling of different lead-based energy materials.

Journal article

Song W, Chen J, Xiaobo J, Zhang X, Xie FE, Riley DJet al., 2016, Dandelion-shape TiO2/Multi-layer Graphene Composed of TiO2(B) Fibrils and Anatase TiO2 Pappi Utilizing Triphase Boundaries for Lithium Storage, Journal of Materials Chemistry A, Vol: 4, Pages: 8762-8768, ISSN: 2050-7496

Three‐dimensional dandelion‐shape TiO2/Multi‐layer graphene compound (TiO2/MLG) composed of TiO2(B) fibrils andanatase pappi structures has been synthesized as potential anode material for Li storage. Electronmicroscopy indicatesthat the composite contains triphase boundaries between anatase, TiO2(B) and graphene, which are responsible for theenhancement of energy storage and the decrease of electrode polarization. Cyclic voltammetric investigations indicatethat both Li+ insertion and pseudocapacitance contribute to charge storage. Ultrahigh specific capacities of 243 and 182mAh g‐1 have been obtained at 0.1 and 1 A g‐1, respectively. Moreover, the excellent capacity retention can reach 99.6%after 100 cycles with almost 100% coulombic efficiency at 0.1 A g‐1. The importance of the triphase boundary in enhancingthe storage of charge and transport of Li+ is demonstrated.

Journal article

Zhang X, Wu X, Centeno A, Ryan M, alford N, riley D, Xie Fet al., 2016, Significant broadband photocurrent enhancement by Au-CZTS core-shell nanostructured photocathodes, Scientific Reports, Vol: 6, ISSN: 2045-2322

Copper zinc tin sulfide (CZTS) is a promising material for harvesting solar energy due to its abundance and non-toxicity. However, its poor performance hinders their wide application. In this paper gold (Au) nanoparticles are successfully incorporated into CZTS to form Au@CZTS core-shell nanostructures. The photocathode of Au@CZTS nanostructures exhibits enhanced optical absorption characteristics and improved incident photon-to-current efficiency (IPCE) performance. It is demonstrated that using this photocathode there is a significant increase of the power conversion efficiency (PCE) of a photoelectrochemical solar cell of 100% compared to using a CZTS without Au core. More importantly, the PCE of Au@CZTS photocathode improved by 15.8% compared to standard platinum (Pt) counter electrode. The increased efficiency is attributed to plasmon resonance energy transfer (PRET) between the Au nanoparticle core and the CZTS shell at wavelengths shorter than the localized surface plasmon resonance (LSPR) peak of the Au and the semiconductor bandgap.

Journal article

Wu X, Zhang X, Price D, Ryan M, Riley J, Alford N, Centeno A, Xie Fet al., 2015, Broadband plasmon photocurrent generation from Au nanoparticles/ mesoporous TiO2 nanotube electrodes, Solar Energy Materials and Solar Cells, Vol: 138, Pages: 80-85, ISSN: 0927-0248

There has been an increasing interest in plasmon-induced enhancement of solar cells and more recently in the direct generation of photocurrent using noble metal nanoparticles with their Localised Surface Plasmon Resonance (LSPR) in the visual part of the spectrum. In this paper we report broadband plasmon photocurrent generation using novel Au nanoparticle incorporated mesoporous TiO2 nanotube electrodes. Plasmonic induced photocurrent due to hot electrons is observed over a broad wavelength range (~500 to 1000 nm). Incident photon-to-electron conversion efficiency (IPCE) measurements undertaken showed a maximum photocurrent enhancement of 200 fold around 700–730 nm wavelength.

Journal article

Donchev E, Pang JS, Gammon PM, Centeno A, Xie F, Petrov PK, Breeze JD, Ryan MP, Riley DJ, McN Net al., 2014, The rectenna device: From theory to practice (a review), MRS Energy and Sustainability, Vol: 1

This review article provides the state-of-art research and developments of the rectenna device and its two main components–the antenna and the rectifier. Furthermore, the history, efficiency trends, and socioeconomic impact of its research are also featured. The rectenna (RECTifying antENNA), which was first demonstrated by William C. Brown in 1964 as a receiver for microwave power transmission, is now increasingly researched as a means of harvesting solar radiation. Tapping into the growing photovoltaic market, the attraction of the rectenna concept is the potential for devices that, in theory, are not limited in efficiency by the Shockley–Queisser limit. In this review, the history and operation of this 40-year old device concept are explored in the context of power transmission and the ever increasing interest in its potential applications at terahertz frequencies, through the infrared and visible spectra. Recent modeling approaches that have predicted controversially high efficiency values at these frequencies are critically examined. It is proposed that to unlock any of the promised potential in the solar rectenna concept, there is a need for each constituent part to be improved beyond the current best performance, with the existing nanometer scale antennas, the rectification and the impedance matching solutions all falling short of the necessary efficiencies at terahertz frequencies. Advances in the fabrication, characterization, and understanding of the antenna and the rectifier are reviewed, and common solar rectenna design approaches are summarized. Finally, the socioeconomic impact of success in this field is discussed and future work is proposed.

Journal article

Donchev E, Pang JS, Gammon PM, Centeno A, Xie F, Petrov PK, Breeze JD, Ryan MP, Riley DJ, Alford NMNet al., 2014, Erratum to: The rectenna device: From theory to practice (a review) — CORRIGENDUM (10.1007/10.1557/mre.2014.6), MRS Energy and Sustainability, Vol: 1

The article contains the following errors: Page 23, left column, line 19. The sentence should read: Another requirement for the insulator is a small dielectric constant since for small area devices the capacitance is reduced, however due to the requirements for tunneling the ultra-thin thicknesses in turn increase capacitance, which has to be kept to a minimum as per Eq. (2). Page 25, left column, line 1. The sentence should read: If the thickness of the higher electron affinity insulator is increased relative to the other insulator, then the QW will be wide enough to form resonant energy levels. The author regrets these errors.

Journal article

Teo GY, Ryan MP, Riley DJ, 2014, A mechanistic study on templated electrodeposition of one-dimensional TiO<sub>2</sub> nanorods and nanotubes using TiOSO<sub>4</sub> as a precursor, ELECTROCHEMISTRY COMMUNICATIONS, Vol: 47, Pages: 13-16, ISSN: 1388-2481

Journal article

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