Khoa H. Ly

Bio: Khoa H. Ly is an academic researcher from Dresden University of Technology. The author has contributed to research in topics: Electrocatalyst & Raman spectroscopy. The author has an hindex of 16, co-authored 31 publications receiving 1063 citations. Previous affiliations of Khoa H. Ly include Technical University of Berlin & University of Cambridge.

Solar-driven reforming of lignocellulose to H 2 with a CdS/CdO x photocatalyst

Abstract: This work was supported by the Christian Doppler Research Association (Austrian Federal Ministry of Science, Research and Economy and the National Foundation for Research, Technology and Development), the OMV Group (to E.R.), the EPSRC (DTA studentships for D.W.W. and T.E.R), the Isaac Newton Trust, the German Research Foundation (to M.F.K.), the World Premier Institute Research Center Initiative (WPI), MEXT, Japan (to K.L.O.) and a Marie Curie Research fellowship (to K.H.L., GAN 701192 - VSHER).

Synergistic electroreduction of carbon dioxide to carbon monoxide on bimetallic layered conjugated metal-organic frameworks

Abstract: Highly effective electrocatalysts promoting CO2 reduction reaction (CO2RR) is extremely desirable to produce value-added chemicals/fuels while addressing current environmental challenges. Herein, we develop a layer-stacked, bimetallic two-dimensional conjugated metal-organic framework (2D c-MOF) with copper-phthalocyanine as ligand (CuN4) and zinc-bis(dihydroxy) complex (ZnO4) as linkage (PcCu-O8-Zn). The PcCu-O8-Zn exhibits high CO selectivity of 88%, turnover frequency of 0.39 s−1 and long-term durability (>10 h), surpassing thus by far reported MOF-based electrocatalysts. The molar H2/CO ratio (1:7 to 4:1) can be tuned by varying metal centers and applied potential, making 2D c-MOFs highly relevant for syngas industry applications. The contrast experiments combined with operando spectroelectrochemistry and theoretical calculation unveil a synergistic catalytic mechanism; ZnO4 complexes act as CO2RR catalytic sites while CuN4 centers promote the protonation of adsorbed CO2 during CO2RR. This work offers a strategy on developing bimetallic MOF electrocatalysts for synergistically catalyzing CO2RR toward syngas synthesis. Effective electrocatalyst is crucial in promoting CO2 reduction to address current energy/environmental issue. Here, the authors develop bimetallic layered two-dimensional conjugated metal-organic framework to synergistically and efficiently electro-catalyze CO2 to CO toward syngas synthesis.

A Phthalocyanine-Based Layered Two-Dimensional Conjugated Metal-Organic Framework as a Highly Efficient Electrocatalyst for the Oxygen Reduction Reaction.

Abstract: Layered two-dimensional (2D) conjugated metal-organic frameworks (MOFs) represent a family of rising electrocatalysts for the oxygen reduction reaction (ORR), due to the controllable architectures, excellent electrical conductivity, and highly exposed well-defined molecular active sites. Herein, we report a copper phthalocyanine based 2D conjugated MOF with square-planar cobalt bis(dihydroxy) complexes (Co-O4 ) as linkages (PcCu-O8 -Co) and layer-stacked structures prepared via solvothermal synthesis. PcCu-O8 -Co 2D MOF mixed with carbon nanotubes exhibits excellent electrocatalytic ORR activity (E1/2 =0.83 V vs. RHE, n=3.93, and jL =5.3 mA cm-2 ) in alkaline media, which is the record value among the reported intrinsic MOF electrocatalysts. Supported by in situ Raman spectro-electrochemistry and theoretical modeling as well as contrast catalytic tests, we identified the cobalt nodes as ORR active sites. Furthermore, when employed as a cathode electrocatalyst for zinc-air batteries, PcCu-O8 -Co delivers a maximum power density of 94 mW cm-2 , outperforming the state-of-the-art Pt/C electrocatalysts (78.3 mW cm-2 ).

A High-Rate Two-Dimensional Polyarylimide Covalent Organic Framework Anode for Aqueous Zn-Ion Energy Storage Devices.

Abstract: Rechargeable aqueous Zn-ion energy storage devices are promising candidates for next-generation energy storage technologies. However, the lack of highly reversible Zn2+-storage anode materials with low potential windows remains a primary concern. Here, we report a two-dimensional polyarylimide covalent organic framework (PI-COF) anode with high-kinetics Zn2+-storage capability. The well-organized pore channels of PI-COF allow the high accessibility of the build-in redox-active carbonyl groups and efficient ion diffusion with a low energy barrier. The constructed PI-COF anode exhibits a specific capacity (332 C g-1 or 92 mAh g-1 at 0.7 A g-1), a high rate capability (79.8% at 7 A g-1), and a long cycle life (85% over 4000 cycles). In situ Raman investigation and first-principle calculations clarify the two-step Zn2+-storage mechanism, in which imide carbonyl groups reversibly form negatively charged enolates. Dendrite-free full Zn-ion devices are fabricated by coupling PI-COF anodes with MnO2 cathodes, delivering excellent energy densities (23.9 ∼ 66.5 Wh kg-1) and supercapacitor-level power densities (133 ∼ 4782 W kg-1). This study demonstrates the feasibility of covalent organic framework as Zn2+-storage anodes and shows a promising prospect for constructing reliable aqueous energy storage devices.

Tuning Product Selectivity for Aqueous CO2 Reduction with a Mn(bipyridine)-pyrene Catalyst Immobilized on a Carbon Nanotube Electrode

Abstract: The development of high-performance electrocatalytic systems for the controlled reduction of CO2 to value-added chemicals is a key goal in emerging renewable energy technologies. The lack of selective and scalable catalysts in aqueous solution currently hampers the implementation of such a process. Here, the assembly of a [MnBr(2,2′-bipyridine)(CO)3] complex anchored to a carbon nanotube electrode via a pyrene unit is reported. Immobilization of the molecular catalyst allows electrocatalytic reduction of CO2 under fully aqueous conditions with a catalytic onset overpotential of η = 360 mV, and controlled potential electrolysis generated more than 1000 turnovers at η = 550 mV. The product selectivity can be tuned by alteration of the catalyst loading on the nanotube surface. CO was observed as the main product at high catalyst loadings, whereas formate was the dominant CO2 reduction product at low catalyst loadings. Using UV–vis and surface-sensitive IR spectroelectrochemical techniques, two different inte...

Particulate Photocatalysts for Light-Driven Water Splitting: Mechanisms, Challenges, and Design Strategies

Abstract: Solar-driven water splitting provides a leading approach to store the abundant yet intermittent solar energy and produce hydrogen as a clean and sustainable energy carrier. A straightforward route to light-driven water splitting is to apply self-supported particulate photocatalysts, which is expected to allow solar hydrogen to be competitive with fossil-fuel-derived hydrogen on a levelized cost basis. More importantly, the powder-based systems can lend themselves to making functional panels on a large scale while retaining the intrinsic activity of the photocatalyst. However, all attempts to generate hydrogen via powder-based solar water-splitting systems to date have unfortunately fallen short of the efficiency values required for practical applications. Photocatalysis on photocatalyst particles involves three sequential steps: (i) absorption of photons with higher energies than the bandgap of the photocatalysts, leading to the excitation of electron-hole pairs in the particles, (ii) charge separation and migration of these photoexcited carriers, and (iii) surface chemical reactions based on these carriers. In this review, we focus on the challenges of each step and summarize material design strategies to overcome the obstacles and limitations. This review illustrates that it is possible to employ the fundamental principles underlying photosynthesis and the tools of chemical and materials science to design and prepare photocatalysts for overall water splitting.

Construction of ZnIn2S4-In2O3 Hierarchical Tubular Heterostructures for Efficient CO2 Photoreduction.

Abstract: We demonstrate the rational design and construction of sandwich-like ZnIn2S4–In2O3 hierarchical tubular heterostructures by growing ZnIn2S4 nanosheets on both inner and outer surfaces of In2O3 microtubes as photocatalysts for efficient CO2 photoreduction. The unique design integrates In2O3 and ZnIn2S4 into hierarchical one-dimensional (1D) open architectures with double-heterojunction shells and ultrathin two-dimensional (2D) nanosheet subunits. This design accelerates the separation and transfer of photogenerated charges, offers large surface area for CO2 adsorption, and exposes abundant active sites for surface catalysis. Benefiting from the structural and compositional merits, the optimized ZnIn2S4–In2O3 photocatalyst exhibits outstanding performance for reductive CO2 deoxygenation with considerable CO generation rate (3075 μmol h–1 g–1) and high stability.

Homogeneously Catalyzed Electroreduction of Carbon Dioxide-Methods, Mechanisms, and Catalysts

Abstract: The utilization of CO2 via electrochemical reduction constitutes a promising approach toward production of value-added chemicals or fuels using intermittent renewable energy sources. For this purpose, molecular electrocatalysts are frequently studied and the recent progress both in tuning of the catalytic properties and in mechanistic understanding is truly remarkable. While in earlier years research efforts were focused on complexes with rare metal centers such as Re, Ru, and Pd, the focus has recently shifted toward earth-abundant transition metals such as Mn, Fe, Co, and Ni. By application of appropriate ligands, these metals have been rendered more than competitive for CO2 reduction compared to the heavier homologues. In addition, the important roles of the second and outer coordination spheres in the catalytic processes have become apparent, and metal–ligand cooperativity has recently become a well-established tool for further tuning of the catalytic behavior. Surprising advances have also been made ...

Metal-Organic Framework-Based Catalysts with Single Metal Sites.

Abstract: Metal-organic frameworks (MOFs) are a class of distinctive porous crystalline materials constructed by metal ions/clusters and organic linkers. Owing to their structural diversity, functional adjustability, and high surface area, different types of MOF-based single metal sites are well exploited, including coordinately unsaturated metal sites from metal nodes and metallolinkers, as well as active metal species immobilized to MOFs. Furthermore, controllable thermal transformation of MOFs can upgrade them to nanomaterials functionalized with active single-atom catalysts (SACs). These unique features of MOFs and their derivatives enable them to serve as a highly versatile platform for catalysis, which has actually been becoming a rapidly developing interdisciplinary research area. In this review, we overview the recent developments of catalysis at single metal sites in MOF-based materials with emphasis on their structures and applications for thermocatalysis, electrocatalysis, and photocatalysis. We also compare the results and summarize the major insights gained from the works in this review, providing the challenges and prospects in this emerging field.

Artificial photosynthesis: opportunities and challenges of molecular catalysts

Abstract: Molecular catalysis plays an essential role in both natural and artificial photosynthesis (AP). However, the field of molecular catalysis for AP has gradually declined in recent years because of doubt about the long-term stability of molecular-catalyst-based devices. This review summarizes the development history of molecular-catalyst-based AP, including the fundamentals of AP, molecular catalysts for water oxidation, proton reduction and CO2 reduction, and molecular-catalyst-based AP devices, and it provides an analysis of the advantages, challenges, and stability of molecular catalysts. With this review, we aim to highlight the following points: (i) an investigation on molecular catalysis is one of the most promising ways to obtain atom-efficient catalysts with outstanding intrinsic activities; (ii) effective heterogenization of molecular catalysts is currently the primary challenge for the application of molecular catalysis in AP devices; (iii) development of molecular catalysts is a promising way to solve the problems of catalysis involved in practical solar fuel production. In molecular-catalysis-based AP, much has been attained, but more challenges remain with regard to long-term stability and heterogenization techniques.