About

Areas of specialism

Materials Characterisation (XRD, XPS, FTIR, SEM, STEM, BET); Product analysis (GC, HPLC, NMR, MS); operando techniques (FTIR, XAS, Raman spectroscopy); Electrocatalysis (HER, OER, CO2RR, alternative feedstock oxidation)

University roles and responsibilities

  • Reviewer for FEPS College of Experts

    Affiliations and memberships

    Member
    Royal Society of Chemistry
    Reviewer
    Energy & Environmental Science (RSC journal)
    Fellow
    Institute for Sustainability
    Member
    Institute of Materials, Minerals and Mining

    Research

    Research interests

    Research projects

    Research collaborations

    Supervision

    Postgraduate research supervision

    Teaching

    Publications

    Y Xu, R Xie, Q Li, J Feng, H Luo, Q Ye, Z Guo, Y Cao, M Palma, G Chai, M-M Titirici, C R Jones (2023)Pyridine Functionalized Carbon Nanotubes: Unveiling the Role of External Pyridinic Nitrogen Sites for Oxygen Reduction Reaction Wiley-VCH GmbH

    Pyridinic nitrogen has been recognized as the primary active site in nitrogen-doped carbon electrocatalysts for the oxygen reduction reaction (ORR), which is a critical process in many renewable energy devices. However, the preparation of nitrogen-doped carbon catalysts comprised of exclusively pyridinic nitrogen remains challenging, as well as understanding the precise ORR mechanisms on the catalyst. Herein, a novel process is developed using pyridyne reactive intermediates to functionalize carbon nanotubes (CNTs) exclusively with pyridine rings for ORR electrocatalysis. The relationship between the structure and ORR performance of the prepared materials is studied in combination with density functional theory calculations to probe the ORR mechanism on the catalyst. Pyridinic nitrogen can contribute to a more efficient 4-electron reaction pathway, while high level of pyridyne functionalization result in negative structural effects, such as poor electrical conductivity, reduced surface area, and small pore diameters, that suppressed the ORR performance. This study provides insights into pyridine-doped CNTs-functionalized for the first time via pyridyne intermediates-as applied in the ORR and is expected to serve as valuable inspiration in designing high-performance electrocatalysts for energy applications.

    Xiaoqiang Liang, Sen Wang, Jingyu Feng, Zhen Xu, Zhenyu Guo, Hui Luo, Feng Zhang, Chen Wen, Lei Feng, Chengan Wan, Maria-Magdalena Titirici (2023)Structural transformation of metal-organic frameworks and identification of electrocatalytically active species during the oxygen evolution reaction under neutral conditions, In: Inorganic chemistry frontiers1(1)pp. 2961-2977 Royal Soc Chemistry

    The electrocatalytic oxygen evolution reaction (OER) under neutral or near-neutral conditions has attracted research interest due to its environmental friendliness and economic sustainability in comparison with currently available acidic and alkaline conditions. However, it is challenging to identify electrocatalytically active species in the OER procedure under neutral environments due to non-crystalline forms of catalysts. Crystalline metal-organic framework (MOF) materials could provide novel insights into electrocatalytically active species because of their well-defined structures. In this study, we synthesized two isostructural two-dimensional (2D) MOFs [Co(HCi)(2)(H2O)(2)center dot 2DMF](n) (Co-Ci-2D) and [Ni(HCi)(2)(H2O)(2)center dot 2DMF](n) (Ni-Ci-2D) (H(2)Ci = 1H-indazole-5-carboxylic acid, DMF = N,N-dimethyl-formamide) to investigate their OER performance in a neutral environment. Our results indicate that Co-Ci-2D holds a current density of 3.93 mA cm(-2) at 1.8 V vs. RHE and an OER durability superior to the benchmark catalyst IrO2. Utilizing the advantages of the structural transformation of MOF materials which are easier to characterize and analyze compared with ill-defined amorphous materials, we found that a mononuclear coordination compound [Co(HCi)(2)(H2O)(4)] (Co-Ci-mono-A) and its isomer (Co-Ci-mono-B) were proved to be active species of Co-Ci-2D in the neutral OER process. For Ni-Ci-2D, mononuclear coordination compounds similar to the structures of the cobalt material (Ni-Ci-mono-A and Ni-Ci-mono-B) together with NiHPO4 formed by the precipitation were confirmed as active species for neutral OER catalysis. Additionally, the difference in OER activities between Co-Ci-2D and Ni-Ci-2D, approximately one order of magnitude, can be attributed to changes in bond strength resulting from variations in bond length within coordination octahedra after being treated with the PBS solution. These findings contribute to a better comprehension of the OER procedure in neutral media.

    Yue Xu, Ruikuan Xie, Qi Li, Jingyu Feng, Hui Luo, Qingyu Ye, Zhenyu Guo, Ye Cao, Matteo Palma, Guoliang Chai, Maria‐Magdalena Titirici, Christopher R Jones (2023)Pyridine Functionalized Carbon Nanotubes: Unveiling the Role of External Pyridinic Nitrogen Sites for Oxygen Reduction Reaction, In: Small (Weinheim an der Bergstrasse, Germany)pp. e2302795-e2302795
    Saurav Ch Sarma, Jesus Barrio, Alexander Bagger, Angus Pedersen, Mengjun Gong, Hui Luo, Mengnan Wang, Silvia Favero, Chang-Xin Zhao, Qiang Zhang, Anthony Kucernak, Maria-Magdalena Titirici, Ifan E. L. Stephens (2023)Reaching the Fundamental Limitation in CO2 Reduction to CO with Single Atom Catalysts, In: Advanced functional materials Wiley

    The electrochemical CO2 reduction reaction (CO2RR) to value-added chemicals with renewable electricity is a promising method to decarbonize parts of the chemical industry. Recently, single metal atoms in nitrogen-doped carbon (MNC) have emerged as potential electrocatalysts for CO2RR to CO with high activity and faradaic efficiency, although the reaction limitation for CO2RR to CO is unclear. To understand the comparison of intrinsic activity of different MNCs, two catalysts are synthesized through a decoupled two-step synthesis approach of high temperature pyrolysis and low temperature metalation (Fe or Ni). The highly meso-porous structure results in the highest reported electrochemical active site utilization based on in situ nitrite stripping; up to 59 +/- 6% for NiNC. Ex situ X-ray absorption spectroscopy (XAS) confirms the penta-coordinated nature of the active sites. The catalysts are amongst the most active in the literature for CO2 reduction to CO. The density functional theory calculations (DFT) show that their binding to the reaction intermediates approximates to that of Au surfaces. However, it is found that the turnover frequencies (TOFs) of the most active catalysts for CO evolution converge, suggesting a fundamental ceiling to the catalytic rates.

    Fei Xie, Zhen Xu, Anders C. S. Jensen, Feixiang Ding, Heather Au, Jingyu Feng, Hui Luo, Mo Qiao, Zhenyu Guo, Yaxiang Lu, Alan J. Drew, Yong-Sheng Hu, Maria-Magdalena Titirici (2019)Unveiling the role of hydrothermal carbon dots as anodes in sodium-ion batteries with ultrahigh initial coulombic efficiency, In: Journal of materials chemistry. A, Materials for energy and sustainability7(48)pp. 27567-27575 Royal Soc Chemistry

    Hard carbon materials are regarded as the most promising anode materials for sodium-ion batteries (SIBs) due to their best cost-effectiveness. However, their relatively low specific capacity and initial Coulombic efficiency (ICE) compared with the graphite anode in lithium-ion batteries still limit the energy density for further development. Thus, it is necessary to produce high-performance hard carbon anode materials with high ICE to improve the SIB technology. Here we show the use of usually ignored carbon dots from the supernatant of hydrothermal carbonization (HTC) as anodes for SIBs after directly drying and carbonization. Compared to traditional HTC carbon spheres from the solid phase, the further carbonized carbon dots exhibit an excellent specific capacity of over 300 mA h g(-1) with a significantly enhanced ICE of up to 91% at 30 mA g(-1) which is among the highest values reported for carbonaceous anodes in SIBs. The superior ICE could benefit a high energy density of 248 W h kg(-1) in full cells with the NaNi1/3Fe1/3Mn1/3O2 cathode. This new discovery from the simple traditional method provides new aspects of designing high-performance SIBs in future commercialization.

    Magda Titirici, Sterling G. Baird, Taylor D. Sparks, Shirley Min Yang, Agnieszka Brandt-Talbot, Omid Hosseinaei, David P. Harper, Richard M. Parker, Silvia Vignolini, Lars A. Berglund, Yuanyuan Li, Huai-Ling Gao, Li-Bo Mao, Shu-Hong Yu, Noel Diez, Guillermo A. Ferrero, Marta Sevilla, Petra Agota Szilagyi, Connor J. Stubbs, Joshua C. Worch, Yunping Huang, Christine K. Luscombe, Koon-Yang Lee, Hui Luo, M. J. Platts, Devendra Tiwari, Dmitry Kovalevskiy, David J. Fermin, Heather Au, Hande Alptekin, Maria Crespo-Ribadeneyra, Valeska P. Ting, Tim-Patrick Fellinger, Jesus Barrio, Olivia Westhead, Claudie Roy, Ifan E. L. Stephens, Sabina Alexandra Nicolae, Saurav Ch Sarma, Rose P. Oates, Chen-Gang Wang, Zibiao Li, Xian Jun Loh, Rupert J. Myers, Niko Heeren, Alice Gregoire, Clement Perisse, Xiaoying Zhao, Yael Vodovotz, Becky Earley, Goran Finnveden, Anna Bjorklund, Gavin D. J. Harper, Allan Walton, Paul A. Anderson (2022)The sustainable materials roadmap, In: JOURNAL OF PHYSICS-MATERIALS5(3) IOP Publishing Ltd

    Over the past 150 years, our ability to produce and transform engineered materials has been responsible for our current high standards of living, especially in developed economies. However, we must carefully think of the effects our addiction to creating and using materials at this fast rate will have on the future generations. The way we currently make and use materials detrimentally affects the planet Earth, creating many severe environmental problems. It affects the next generations by putting in danger the future of the economy, energy, and climate. We are at the point where something must drastically change, and it must change now. We must create more sustainable materials alternatives using natural raw materials and inspiration from nature while making sure not to deplete important resources, i.e. in competition with the food chain supply. We must use less materials, eliminate the use of toxic materials and create a circular materials economy where reuse and recycle are priorities. We must develop sustainable methods for materials recycling and encourage design for disassembly. We must look across the whole materials life cycle from raw resources till end of life and apply thorough life cycle assessments (LCAs) based on reliable and relevant data to quantify sustainability. We need to seriously start thinking of where our future materials will come from and how could we track them, given that we are confronted with resource scarcity and geographical constrains. This is particularly important for the development of new and sustainable energy technologies, key to our transition to net zero. Currently 'critical materials' are central components of sustainable energy systems because they are the best performing. A few examples include the permanent magnets based on rare earth metals (Dy, Nd, Pr) used in wind turbines, Li and Co in Li-ion batteries, Pt and Ir in fuel cells and electrolysers, Si in solar cells just to mention a few. These materials are classified as 'critical' by the European Union and Department of Energy. Except in sustainable energy, materials are also key components in packaging, construction, and textile industry along with many other industrial sectors. This roadmap authored by prominent researchers working across disciplines in the very important field of sustainable materials is intended to highlight the outstanding issues that must be addressed and provide an insight into the pathways towards solving them adopted by the sustainable materials community. In compiling this roadmap, we hope to aid the development of the wider sustainable materials research community, providing a guide for academia, industry, government, and funding agencies in this critically important and rapidly developing research space which is key to future sustainability.

    Muhammad Aslam, Miriam Navlani-García, Diego Cazorla-Amorós, Hui Luo (2024)Efficient and selective glycerol electrolysis for the co-production of lactic acid and hydrogen with multi-component Pt/C-zeolite catalyst, In: JPhys materials7(1) IOP Publishing

    Among various electrochemical reactions to produce fuels and chemicals, glycerol electrolysis to co-produce hydrogen and lactic acid has received great attention. However, studies have shown the benchmark Pt based catalysts are insufficient in selectively catalysing the glycerol to lactic acid transformation, resulting in a low yield of lactic acid. Here we report a study on glycerol electrolysis with anion-exchange membrane electrode assembly electrolyser. The reaction conditions including mass transport, temperature, current density and KOH concentration were optimised, among which temperature played a significant role in facilitating the reaction rate and thermodynamics. With the optimised condition a multicomponent Pt/C-zeolite electrocatalyst system (Pt/C-CBV600) was developed and tested, which is capable to increase the lactic acid selectivity to 57.3% from the 33.8% with standalone Pt/C. Although the detailed mechanism required further investigation, it is hypothesised that the CBV600 zeolite with abundant Lewis acid surface sites can effectively bind the dihydroxyacetone intermediate, and drive the reaction towards pyruvaldehyde heterogeneously, the key step to form lactic acid.

    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 (2021)Iron, Nitrogen Co-Doped Carbon Spheres as Low Cost, Scalable Electrocatalysts for the Oxygen Reduction Reaction, In: Advanced functional materials31(46)pp. 2102974-n/a Wiley

    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.

    Sabina A. Nicolae, Heather Au, Pierpaolo Modugno, Hui Luo, Anthony E. Szego, Mo Qiao, Liang Li, Wang Yin, Hero J. Heeres, Nicole Berge, Maria-Magdalena Titirici (2020)Recent advances in hydrothermal carbonisation: from tailored carbon materials and biochemicals to applications and bioenergy, In: Green chemistry : an international journal and green chemistry resource : GC22(15)pp. 4747-4800 Royal Soc Chemistry

    Introduced in the literature in 1913 by Bergius, who at the time was studying biomass coalification, hydrothermal carbonisation, as many other technologies based on renewables, was forgotten during the "industrial revolution". It was rediscovered back in 2005, on the one hand, to follow the trend set by Bergius of biomass to coal conversion for decentralised energy generation, and on the other hand as a novel green method to prepare advanced carbon materials and chemicals from biomass in water, at mild temperature, for energy storage and conversion and environmental protection. In this review, we will present an overview on the latest trends in hydrothermal carbonisation including biomass to bioenergy conversion, upgrading of hydrothermal carbons to fuels over heterogeneous catalysts, advanced carbon materials and their applications in batteries, electrocatalysis and heterogeneous catalysis and finally an analysis of the chemicals in the liquid phase as well as a new family of fluorescent nanomaterials formed at the interface between the liquid and solid phases, known as hydrothermal carbon nanodots.

    Hui Luo, Victor Y. Yukuhiro, Pablo S. Fernandez, Jingyu Feng, Paul Thompson, Reshma R. Rao, Rongsheng Cai, Silvia Favero, Sarah J. Haigh, James R. Durrant, Ifan E. L. Stephens, Maria-Magdalena Titirici (2022)Role of Ni in PtNi Bimetallic Electrocatalysts for Hydrogen and Value-Added Chemicals Coproduction via Glycerol Electrooxidation, In: ACS catalysis12(23)pp. 14492-14506 Amer Chemical Soc

    Pt-based bimetallic electrocatalysts are promising candidates to convert surplus glycerol from the biodiesel industry to value-added chemicals and coproduce hydrogen. It is expected that the nature and content of the elements in the bimetallic catalyst can not only affect the reaction kinetics but also influence the product selectivity, providing a way to increase the yield of the desired products. Hence, in this work, we investigate the electrochemical oxidation of glycerol on a series of PtNi nanoparticles with increasing Ni content using a combination of physicochemical structural analysis, electrochemical measurements, operando spectroscopic techniques, and advanced product characterizations. With a moderate Ni content and a homogenously alloyed bimetallic Pt-Ni structure, the PtNi2 catalyst displayed the highest reaction activity among all materials studied in this work. In situ FTIR data show that PtNi2 can activate the glycerol molecule at a more negative potential (0.4 VRHE) than the other PtNi catalysts. In addition, its surface can effectively catalyze the complete C-C bond cleavage, resulting in lower CO poisoning and higher stability. Operando X-ray absorption spectroscopy and UV-vis spectroscopy suggest that glycerol adsorbs strongly onto surface Ni(OH)x sites, preventing their oxidation and activation of oxygen or hydroxyl from water. As such, we propose that the role of Ni in PtNi toward glycerol oxidation is to tailor the electronic structure of the pure Pt sites rather than a bifunctional mechanism. Our experiments provide guidance for the development of bimetallic catalysts toward highly efficient, selective, and stable glycerol oxidation reactions.

    Shaohui Guo, Hui Luo, Xiaochuan Duan, Bingqing Wei, Xianming Zhang (2022)Plasma-Wind-Assisted In2S3 Preparation with an Amorphous Surface Structure for Enhanced Photocatalytic Hydrogen Production, In: Nanomaterials (Basel, Switzerland)12(10) MDPI

    Photocatalytic production from water is considered an effective solution to fossil fuel-related environmental concerns, and photocatalyst surface science holds a significant interest in balancing photocatalysts’ stability and activity. We propose a plasma-wind method to tune the surface properties of a photocatalyst with an amorphous structure. Theoretical calculation shows that the amorphous surface structure can cause an unsaturated coordination environment to adjust the electron distribution, forming more adsorption sites. Thus, the photocatalyst with a crystal–amorphous (C–A) interface can strengthen light absorption, harvest photo-induced electrons, and enrich the active sites, which help improve hydrogen yield. As a proof of concept, with indium sulfide (In 2 S 3 ) nanosheets used as the catalyst, an impressive hydrogen production rate up to 457.35 μmol cm −2 h −1 has been achieved. Moreover, after plasma-assisted treatment, In 2 S 3 with a C–A interface can produce hydrogen from water under natural outdoor conditions. Following a six-hour test, the rate of photocatalytic hydrogen evolution is found to be 400.50 μmol cm −2 g −1 , which demonstrates that a catalyst prepared through plasma treatment is both effective and highly practical.

    Jesús 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 (2022)Metal coordination in C 2 N-like materials towards dual atom catalysts for oxygen reduction, In: Journal of materials chemistry. A, Materials for energy and sustainability10(11)pp. 6023-6030

    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 C N-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 g at 0.8 V 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.

    Hui Luo, Stoichko Dimitrov, Matyas Daboczi, Ji-Seon Kim, Qian Guo, Yuanxing Fang, Marc-Antoine Stoeckel, Paolo Samori, Oliver Fenwick, Ana Belen Jorge Sobrido, Xinchen Wang, Maria-Magdalena Titirici (2020)Nitrogen-Doped Carbon Dots/TiO2 Nanoparticle Composites for Photoelectrochemical Water Oxidation, In: ACS applied nano materials3(4)pp. 3371-3381 Amer Chemical Soc

    Carbon dots on photoactive semiconductor nanomaterials have represented an effective strategy for enhancing their photoelectrochemical (PEC) activity. By carefully designing and manipulating a carbon dot/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 of PEC devices. To address this need of improving the fundamental understanding of the 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 ultraviolet 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 hybridization of NCDs and TiO2 is able not only to extend TiO2 light response into the visible range but also to form a heterojunction at the NCDs/TiO2 interface with a 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 the carbon dot-TiO2 nanoparticle composite in a PEC system for understanding the energy-transfer mechanism, demonstrating the favorable role of NCDs in the photocurrent response of TiO2 for the water oxidation process. This study reveals the importance of combining structural, photophysical, and electrochemical experiments to develop a comprehensive understanding of the nanoscale charge-transfer processes between the carbon dots and their catalyst supports.

    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 (2020)Pt single-atoms supported on nitrogen-doped carbon dots for highly efficient photocatalytic hydrogen generation, In: Journal of materials chemistry. A, Materials for energy and sustainability8(29)pp. 14690-14696 Royal Soc Chemistry

    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 TiO(2)to achieve high hydrogen generation activity and to understand the fundamentals at the Pt/NCD/TiO(2)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 H(2)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.

    Barun Chakrabarti, Vladimir Yufit, Ashkan Kavei, Yuhua Xia, Graham Stevenson, Evangelos Kalamaras, Hui Luo, Jingyu Feng, Farid Tariq, Oluwadamilola Taiwo, Maria -Magdalena Titirici, Nigel Brandon (2019)Charge/discharge and cycling performance of flexible carbon paper electrodes in a regenerative hydrogen/vanadium fuel cell, In: International journal of hydrogen energy44(57)pp. 30093-30107 Elsevier

    The regenerative hydrogen/vanadium fuel cell (RHVFC) is investigated with Freudenberg carbon paper electrodes (CPs). Along with thermal treatment, the Freudenberg CPs are also treated with reduced graphene oxide (rGO) using electrophoretic deposition at 300 V. The rGO modified CP results in 25% higher power density than its untreated counterpart under the same operating conditions. In comparison to the first preliminary study, the power density reported herein is more than four times higher. Additionally, the Freudenberg CPs modified with heat treatment followed by rGO deposition facing the membrane (rGOHTFM) provide the best electrolyte discharge utilization (UE) of 99%, followed by untreated (98%) and heat treated samples (97%) at 50 mA cm(-2). The rGOHTFM also record high charge and discharge energy efficiencies (eta(E)) of 93% at the same current density, which is slightly higher than untreated CPs (eta(E) = 91%). Cycling the system 10 times also results in higher eta(E) and UE for rGOHTFM CP (eta(E) = 92% and UE = 99% on average) in comparison to untreated electrodes (eta(E) = 86% and UE = 97% on average). In comparison the widely investigated SGL 10AA CP has lower efficiencies and utilization as expected (eta(E) = 74% and UE = 83% on average). (C) 2019 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

    Hui Luo, Jesus Barrio, Nixon Sunny, Alain Li, Ludmilla Steier, Nilay Shah, Ifan E. L. Stephens, Maria-Magdalena Titirici (2021)Progress and Perspectives in Photo- and Electrochemical-Oxidation of Biomass for Sustainable Chemicals and Hydrogen Production, In: Advanced energy materials11(43)pp. 2101180-n/a Wiley

    Biomass is recognized as an ideal CO2 neutral, abundant, and renewable resource substitute to fossil fuels. The rich proton content in most biomass derived materials, such as ethanol, 5-hydroxymethylfurfural (HMF) and glycerol allows it to be an effective hydrogen carrier. The oxidation derivatives, such as 2,5-difurandicarboxylic acid from HMF, glyceric acid from glycerol are valuable products to be used in biodegradable polymers and pharmaceuticals. Therefore, combining biomass-derived compound oxidation at the anode and hydrogen evolution reaction at the cathode in a biomass electrolysis or photo-reforming reactor would present a promising strategy for coproducing high value chemicals and hydrogen with low energy consumption and CO2 emissions. This review aims to combine fundamental knowledge on photo and electro-assisted catalysis to provide a comprehensive understanding of the general reaction mechanisms of different biomass-derived molecule oxidation. At the same time, catalyst requirements and recent advances for various feedstock compounds are also reviewed in detail. Technoeconomic assessment and life cycle analysis are performed on various feedstocks to assess the relative benefits of various processes, and finally critical prospects are given on the challenges and opportunities for technology development to meet the sustainability requirement of the future global energy economy.

    Ying Tu, Candice Kyle, Hui Luo, De-Wen Zhang, Anirban Das, Joe Briscoe, Steve Dunn, Maria-Magdalena Titirici, Steffi Krause (2020)Ammonia Gas Sensor Response of a Vertical Zinc Oxide Nanorod-Gold Junction Diode at Room Temperature, In: ACS sensors5(11)pp. 3568-3575

    Conventional metal oxide semiconductor (MOS) gas sensors have been investigated for decades to protect our life and property. However, the traditional devices can hardly fulfill the requirements of our fast developing mobile society, because the high operating temperatures greatly limit their applications in battery-loaded portable systems that can only drive devices with low power consumption. As ammonia is gaining importance in the production and storage of hydrogen, there is an increasing demand for energy-efficient ammonia detectors. Hence, in this work, a Schottky diode resulting from the contact between zinc oxide nanorods and gold is designed to detect gaseous ammonia at room temperature with a power consumption of 625 μW. The Schottky diode gas sensors benefit from the change of barrier height in different gases as well as the catalytic effect of gold nanoparticles. This diode structure, fabricated without expensive interdigitated electrodes and displaying excellent performance at room temperature, provides a novel method to equip mobile devices with MOS gas sensors.

    Hui Luo, Leonardo Lari, Hyunjeong Kim, Servann Hérou, Liviu Cristian Tanase, Vlado K. Lazarov, Maria-Magdalena Titirici (2022)Structural evolution of carbon dots during low temperature pyrolysis, In: Nanoscale14(3)pp. 910-918

    Carbon dots (CDs) are an emerging class of photoluminescent material. Their unique optical properties arise from the discrete energy levels in their electronic states, which directly relate to their crystalline and chemical structure. It is expected that when CDs go through structural changes via chemical reduction or thermal annealing, their energy levels will be altered, inducing unique optoelectronic properties such as solid-state photoluminescence (PL). However, the detailed structural evolution and how the optoelectronic characteristics of CDs are affected remain unclear. Therefore, it is of fundamental interest to understand how the structure of CDs prepared by hydrothermal carbonisation (HTC) rearranges from a highly functionalised disordered structure into a more ordered graphitic structure. In this paper, detailed structural characterisation and in situ TEM were conducted to reveal the structural evolution of CDs during the carbonisation process, which have demonstrated a growth in aromatic domains and reduction in oxidation sites. These structural features are correlated with their near-infrared (NIR) solid-state PL properties, which may find a lot of practical applications such as temperature sensing, solid-state display lighting and anti-counterfeit security inks.

    Hui Luo, Qian Guo, Petra Ágota Szilágyi, Ana Belen Jorge, Maria-Magdalena Titirici (2020)Carbon Dots in Solar-to-Hydrogen Conversion, In: Trends in chemistry2(7)pp. 623-637 Elsevier Inc

    Solar hydrogen production from catalytic water splitting is one of the many options available to help generate clean power and alleviate the threatening environmental concerns stemming from the use of fossil fuels. During the past decade, carbon dots (CDs) have shown great potential in their application for solar-driven hydrogen production owing to their exceptional photophysical and electrical properties derived from their sp2/sp3 hybridized core structure and rich surface functionality. In this review, we correlate the structural features of CDs with their optical and electronic properties and evaluate key properties for efficient solar energy-conversion applications with an emphasis on photocatalysis and photoelectrocatalysis, to shed some light on designing high performance CD-based photosystems. Carbon dots (CDs) have found increasing application in solar-to-hydrogen conversion due to their low cost, low toxicity, and exceptional optoelectronic properties.Structure–property correlations in different CD systems have been developed, providing clear guidance for future investigations. CDs with desired physicochemical properties can be fabricated though structure manipulation.CDs have shown significant promise as photosensitizers, electron acceptors, electron donors, hole extractors, and cocatalysts in solar hydrogen production through water-splitting.

    De-Wen Zhang, Nikolaos Papaioannou, Naomi Michelle David, Hui Luo, Hui Gao, Liviu Cristian Tanase, Thibault Degousee, Paolo Samori, Andrei Sapelkin, Oliver Fenwick, Maria-Magdalena Titirici, Steffi Krause (2018)Photoelectrochemical response of carbon dots (CDs) derived from chitosan and their use in electrochemical imaging, In: Materials horizons5(3)pp. 423-428 Royal Soc Chemistry

    We report a direct photoelectrochemical response from low cost carbon dots (CDs) prepared from chitosan via a solvothermal method. The carbon dots were covalently linked to an indium tin oxide (ITO) surface through a self-assembled silane monolayer. We attribute the photocurrent of the ITO-silane-CD surface to a photogenerated electron-transfer process by CDs under illumination with a wavelength of 420 nm to 450 nm. The self-assembled monolayer of CDs was used for ac-photocurrent imaging of the surface with micron scale lateral resolution. This discovery opens up new applications for CDs as biocompatible, light-addressable electrochemical sensors in bioanalytical and bioimaging applications.

    James King, Linda Zhang, Szymon Doszczeczko, Olga Sambalova, Hui Luo, Fadli Rohman, Omotoyosi Phillips, Andreas Borgschulte, Michael Hirscher, Matthew Addicoat, Petra Ágota Szilágyi (2020)How to functionalise metal–organic frameworks to enable guest nanocluster embedment, In: Journal of materials chemistry. A, Materials for energy and sustainability8(9)pp. 4889-4897

    We report on the development and verification of an enhanced computational model capable of robust predictions and yielding a single descriptor to the successful embedding of guest nanoclusters into the pores of functionalised metal–organic frameworks. Using the predictions of this model, we have been able to embed Pd nanoclusters in the pores of Br-UiO-66 and show that the embedding of Pd nanoclusters in both (OH) 2 -UiO-66 and (Cl) 2 -UiO-66 is not successful. Also, using various independent methods, we identified the strong host–guest interactions that anchor the guest nanoclusters inside the Br-UiO-66 framework which result in the surface modification of said nanoclusters. We demonstrated that the level of this surface modification is a direct function of the framework functional groups. This new approach for the rational design of nanocluster–metal–organic framework systems, and a demonstrated tool box for their characterisation, will promote the exploitation of surface modification of nanoclusters via their embedding into functionalised metal–organic framework pores.

    Jesus Barrio, Angus Pedersen, Silvia Favero, Hui Luo, Mengnan Wang, Saurav Ch Sarma, Jingyu Feng, Linh Tran Thi Ngoc, Simon Kellner, Alain You Li, Ana Belen Jorge Sobrido, Maria-Magdalena Titirici (2023)Bioinspired and Bioderived Aqueous Electrocatalysis, In: Chemical reviews123(5)pp. 2311-2348 Amer Chemical Soc

    The development of efficient and sustainable electrochemical systems able to provide clean-energy fuels and chemicals is one of the main current challenges of materials science and engineering. Over the last decades, significant advances have been made in the development of robust electrocatalysts for different reactions, with fundamental insights from both computational and experimental work. Some of the most promising systems in the literature are based on expensive and scarce platinum-group metals; however, natural enzymes show the highest per-site catalytic activities, while their active sites are based exclusively on earth-abundant metals. Additionally, natural biomass provides a valuable feedstock for producing advanced carbonaceous materials with porous hierarchical structures. Utilizing resources and design inspiration from nature can help create more sustainable and cost-effective strategies for manufacturing cost-effective, sustainable, and robust electrochemical materials and devices. This review spans from materials to device engineering; we initially discuss the design of carbon-based materials with bioinspired features (such as enzyme active sites), the utilization of biomass resources to construct tailored carbon materials, and their activity in aqueous electrocatalysis for water splitting, oxygen reduction, and CO2 reduction. We then delve in the applicability of bioinspired features in electrochemical devices, such as the engineering of bioinspired mass transport and electrode interfaces. Finally, we address remaining challenges, such as the stability of bioinspired active sites or the activity of metal-free carbon materials, and discuss new potential research directions that can open the gates to the implementation of bioinspired sustainable materials in electrochemical devices.

    Mo Qiao, Guillermo A. Ferrero, Leticia Fernandez Velasco, Wei Vern Hor, Yan Yang, Hui Luo, Peter Lodewyckx, Antonio B. Fuertes, Marta Sevilla, Maria-Magdalena Titirici (2019)Boosting the Oxygen Reduction Electrocatalytic Performance of Nonprecious Metal Nanocarbons via Triple Boundary Engineering Using Protic Ionic Liquids, In: ACS applied materials & interfaces11(12)pp. 11298-11305 Amer Chemical Soc

    The oxygen reduction reaction (ORR) in aqueous media plays a critical role in sustainable and clean energy technologies such as polymer electrolyte membrane and alkaline fuel cells. In this work, we present a new concept to improve the ORR performance by engineering the interface reaction at the electrocatalyst/electrolyte/oxygen triple-phase boundary using a protic and hydrophobic ionic liquid and demonstrate the wide and general applicability of this concept to several Pt-free catalysts. Two catalysts, Fe-N codoped and metal-free N-doped carbon electrocatalysts, are used as a proof of concept. The ionic liquid layer grafted at the nanocarbon surface creates a water-equilibrated secondary reaction medium with a higher O-2 affinity toward oxygen adsorption, promoting the diffusion toward the catalytic active site, while its protic character provides sufficient H+/H3O+ conductivity, and the hydrophobic nature prevents the resulting reaction product water from accumulating and blocking the interface. Our strategy brings obvious improvements in the ORR performance in both acid and alkaline electrolytes, while the catalytic activity of FeNC-nanocarbon outperforms commercial Pt-C in alkaline electrolytes. We believe that this research will pave new routes toward the development of high-performance ORR catalysts free of noble metals via careful interface engineering at the triple point.

    Shaohui Guo, Jie Su, Hui Luo, Xiaochuan Duan, Qianqian Shen, Jinbo Xue, Bingqing Wei, Xian-Ming Zhang (2023)Boosting Photocatalytic Hydrogen Evolution Reaction by the Improved Mass Flow and Energy Flow Process Based on Ultrasound Waves, In: ACS catalysis13(1)pp. 296-307 Amer Chemical Soc

    Sun-driven photocatalytic hydrogen production reaction opens up possibilities for renewable energy systems. The reaction is the mass and energy conversion process between materials and the environment. Thus, the proper physical field introduction is the desired serious consideration to improve the mass flow and energy flow process. Here, we propose a piezo-enhanced photocatalytic system based on the ultrasound field to realize the adjustable built-in electric field favoring photo-induced carriers' transfer. As a proof of concept, the piezo-photocatalyst is prepared through a hydrothermal method. On the basis of the photoelectric characterization and theory calculation, the dynamics of mass transfer is enhanced by the ultrasonic field's spatial compression and cavitation effect. Moreover, the surface redox reaction is accelerated because the chemical bond break-reformation process is improved under the support of the cavitation effect. Thus, an impressive hydrogen production rate of up to 13.09 mmol h-1 g-1 has been achieved with a ternary catalyst. A practical demonstration is also designed to actualize hydrogen production in the natural condition, proving the piezo-photocatalytic system's practical advantages.

    Xinhua Liu, Xiaojuan Qian, Weiqiang Tang, Hui Luo, Yan Zhao, Rui Tan, Mo Qiao, Xinlei Gao, Yang Hua, Huizhi Wang, Shuangliang Zhao, Chao Lai, Magda Titirici, Nigel P. Brandon, Shichun Yang, Billy Wu (2021)Designer uniform Li plating/stripping through lithium–cobalt alloying hierarchical scaffolds for scalable high-performance lithium-metal anodes, In: Journal of energy chemistry52pp. 385-392 Elsevier B.V

    Lithium metal anodes are of great interest for advanced high-energy density batteries such as lithium-air, lithium-sulfur and solid-state batteries, due to their low electrode potential and ultra-high theoretical capacity. There are, however, several challenges limiting their practical applications, which include low coulombic efficiency, the uncontrollable growth of dendrites and poor rate capability. Here, a rational design of 3D structured lithium metal anodes comprising of in-situ growth of cobalt-decorated nitrogen-doped carbon nanotubes on continuous carbon nanofibers is demonstrated via electrospinning. The porous and free-standing scaffold can enhance the tolerance to stresses resulting from the intrinsic volume change during Li plating/stripping, delivering a significant boost in both charge/discharge rates and stable cycling performance. A binary Co-Li alloying phase was generated at the initial discharge process, creating more active sites for the Li nucleation and uniform deposition. Characterization and density functional theory calculations show that the conductive and uniformly distributed cobalt-decorated carbon nanotubes with hierarchical structure can effectively reduce the local current density and more easily absorb Li atoms, leading to more uniform Li nucleation during plating. The current work presents an advance on scalable and cost-effective strategies for novel electrode materials with 3D hierarchical microstructures and mechanical flexibility for lithium metal anodes. Hierarchical carbon-metal scaffolds, containing Co nanoparticles encapsulated in nitrogen-doped carbon nanotubes grown in carbon nanofibers, were used as lithium metal anodes which can promote evenly distributed Li, suppress Li dendrites and stabilize cycling performance. [Display omitted]

    Fei Xie, Zhen Xu, Zhenyu Guo, Anders C. S. Jensen, Jingyu Feng, Hui Luo, Feixiang Ding, Yaxiang Lu, Yong-Sheng Hu, Maria-Magdalena Titirici (2022)Achieving high initial Coulombic efficiency for competent Na storage by microstructure tailoring from chiral nematic nanocrystalline cellulose, In: Carbon energy4(5)pp. 914-923 Wiley

    Although it has been proven that porous, heteroatomic, and defective structures improve Na storage performance, they also severely affect the initial Coulombic efficiency (ICE) due to the huge irreversible capacity in the first cycle, which always limits the practical application of carbon anodes in commercial Na-ion batteries (NIBs). Here, we show the successful synthesis of nanocrystalline cellulose and the derivative hard carbons. A series of treatments including acid hydrolysis, hydrothermal carbonization, and high-temperature pyrolysis help tune the pores, heteroatoms, and defects to achieve an optimized balance between superior ICE and reversible capacity of up to 90.4% and 314 mAh g(-1). This study highlights that tailoring the electrode microstructure could be an important strategy in the future design of carbonaceous anode materials for high-performance Na-ion batteries.

    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 (2020)The role of carbon dots - derived underlayer in hematite photoanodes, In: Nanoscale12(39)pp. 20220-20229 Royal Soc Chemistry

    Hematite is a promising candidate as photoanode for solar-driven water splitting, with a theoretically predicted maximum solar-to-hydrogen conversion efficiency of similar to 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 Vvs.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.

    Barun Kumar Chakrabarti, Jingyu Feng, Evangelos Kalamaras, J. Rubio-Garcia, Chandramohan George, Hui Luo, Yuhua Xia, Vladimir Yufit, Maria-Magdalena Titirici, Chee Tong John Low, Anthony Kucernak, Nigel P. Brandon (2020)Hybrid Redox Flow Cells with Enhanced Electrochemical Performance via Binderless and Electrophoretically Deposited Nitrogen-Doped Graphene on Carbon Paper Electrodes, In: ACS applied materials & interfaces12(48)pp. 53869-53878
    Alain Y. Li, Angus Pedersen, Jingyu Feng, Hui Luo, Jesus Barrio, Julien Roman, King Kuok (Mimi) Hii, Maria-Magdalena Titirici (2022)From haemoglobin to single-site hydrogenation catalyst, In: Green chemistry : an international journal and green chemistry resource : GC24(19)pp. 7574-7583 Royal Soc Chemistry

    Iron-based single-site catalysts hold immense potential for achieving highly selective chemical processes, with the added advantage of iron being an earth-abundant metal. They are widely explored in electrocatalysis for oxygen reduction and display promising catalytic activity for organic transformations. In particular, FeNx@C catalysts are active for the reduction of nitroarene into aromatic amines. Yet, they are difficult to mass-produce, and most preparation methods fail to avoid single site aggregation. Here we prepared FeNx@C catalysts from bio-derived compounds, xylose and haemoglobin, in a simple two-step process. Since haemoglobin naturally contains FeNx single-sites, we successfully repurposed them into hydrogenation catalytic centers and avoided their aggregation during the preparation of the material. Their single-site nature was demonstrated by aberration-corrected transmission electron microscopy and X-ray absorption techniques. They were shown to be active for transfer hydrogenation of nitroarenes into anilines, with excellent substrate selectivity and recyclability, as demonstrated by the preserved yield across seven catalytic cycles. We also showed that FeNx@C could be used to prepare 2-phenylbenzimidazole through a reduction/condensation tandem. Our work shows for the first time the viability of biomass precursors to prepare Fe single-site hydrogenation catalysts.

    Servann Herou, Maria Crespo Ribadeneyra, Philipp Schlee, Hui Luo, Liviu Cristian Tanase, Christine Rossberg, Magdalena Titirici (2021)The impact of having an oxygen-rich microporous surface in carbon electrodes for high-power aqueous supercapacitors, In: Journal of energy chemistry53pp. 36-48 Elsevier

    The growth of electrical transportation is crucially important to mitigate rising climate change concerns regarding materials supply. Supercapacitors are high-power devices, particularly suitable for public transportation since they can easily store breaking energy due to their high-rate charging ability. Additionally, they can function with two carbon electrodes, which is an advantage due to the abundance of carbon in biomass and other waste materials (i.e., plastic waste). Newly developed supercapacitive nanocarbons display extremely narrow micropores (0.8 nm), as it increases drastically the capacitance in aqueous electrolytes. Here, we present a strategy to produce low-cost flexible microporous electrodes with extremely high power density (100 kW kg(-1)), using fourty times less activating agent than traditionnal chemically activated carbons. We also demonstrate that the affinity between the carbon and the electrolyte is of paramount importance to maintain rapid ionic diffusion in narrow micropores. Finally, this facile synthesis method shows that low-cost and bio-based free-standing electrode materials with reliable supercapacitive performances can be used in electrochemistry. (C) 2020 Science Press and Dalian Institute of Chemical Physics, Chinese Academy of Sciences. Published by ELSEVIER B.V. and Science Press. All rights reserved.

    Hui Luo, Nikolaos Papaioannou, Enrico Salvadori, Maxie M. Roessler, Gereon Ploenes, Ernst R. H. Eck, Liviu C. Tanase, Jingyu Feng, Yiwei Sun, Yan Yang, Mohsen Danaie, Ana Belen Jorge, Andrei Sapelkin, James Durrant, Stoichko D. Dimitrov, Maria‐Magdalena Titirici (2019)Manipulating the Optical Properties of Carbon Dots by Fine‐Tuning their Structural Features, In: ChemSusChem12(19)pp. 4432-4441
    Wei Xiong, Harshit Porwal, Hui Luo, Vicente Araullo-Peters, Jingyu Feng, Maria-Magdalena Titirici, Michael J. Reece, Joe Briscoe (2020)Photocatalytic activity of 2D nanosheets of ferroelectric Dion-Jacobson compounds, In: Journal of materials chemistry. A, Materials for energy and sustainability8(14)pp. 6564-6568 Royal Soc Chemistry

    Dion-Jacobson compounds have a layered perovskite structure, and a small number of them have been identified as being ferroelectric. Here, RbBiNb2O7 powders are made by conventional solid-state synthesis. The relatively large Rb ion produces an interlayer within the structure with a large spacing and weak bonding. This work shows for the first time that a polar layered perovskite can be exfoliated into 2D nanosheets using a facile and scalable method, namely liquid-phase sonication. With both 2D materials and ferroelectrics being of interest for photocatalysis, the photocatalytic performance of RbBiNb2O7 nanosheets is characterized by measuring its dye degradation rate under a solar simulator. It is demonstrated that the RbBiNb2O7 nanosheet material effectively decolourizes Rhodamine B under visible illumination even though it has a wide bandgap (3.45 eV), and that its photocatalytic activity is greatly enhanced (similar to 4 times faster) when decorated with photodeposited Ag nanoparticles. Reducing the nanosheet size also increases the photocatalytic performance. This work demonstrates that polar 2D Dion-Jacobson phase RbBiNb2O7 is a promising candidate for photocatalytic applications. Further improvements are possible by identifying compounds with a narrower bandgap as a broad compositional window is available in this family of compounds.

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