| 1. |
- Backes, Claudia, et al.
(författare)
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Production and processing of graphene and related materials
- 2020
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Ingår i: 2D Materials. - : IOP Publishing. - 2053-1583. ; 7:2
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Tidskriftsartikel (refereegranskat)abstract
- We present an overview of the main techniques for production and processing of graphene and related materials (GRMs), as well as the key characterization procedures. We adopt a 'hands-on' approach, providing practical details and procedures as derived from literature as well as from the authors' experience, in order to enable the reader to reproduce the results. Section I is devoted to 'bottom up' approaches, whereby individual constituents are pieced together into more complex structures. We consider graphene nanoribbons (GNRs) produced either by solution processing or by on-surface synthesis in ultra high vacuum (UHV), as well carbon nanomembranes (CNM). Production of a variety of GNRs with tailored band gaps and edge shapes is now possible. CNMs can be tuned in terms of porosity, crystallinity and electronic behaviour. Section II covers 'top down' techniques. These rely on breaking down of a layered precursor, in the graphene case usually natural crystals like graphite or artificially synthesized materials, such as highly oriented pyrolythic graphite, monolayers or few layers (FL) flakes. The main focus of this section is on various exfoliation techniques in a liquid media, either intercalation or liquid phase exfoliation (LPE). The choice of precursor, exfoliation method, medium as well as the control of parameters such as time or temperature are crucial. A definite choice of parameters and conditions yields a particular material with specific properties that makes it more suitable for a targeted application. We cover protocols for the graphitic precursors to graphene oxide (GO). This is an important material for a range of applications in biomedicine, energy storage, nanocomposites, etc. Hummers' and modified Hummers' methods are used to make GO that subsequently can be reduced to obtain reduced graphene oxide (RGO) with a variety of strategies. GO flakes are also employed to prepare three-dimensional (3d) low density structures, such as sponges, foams, hydro- or aerogels. The assembly of flakes into 3d structures can provide improved mechanical properties. Aerogels with a highly open structure, with interconnected hierarchical pores, can enhance the accessibility to the whole surface area, as relevant for a number of applications, such as energy storage. The main recipes to yield graphite intercalation compounds (GICs) are also discussed. GICs are suitable precursors for covalent functionalization of graphene, but can also be used for the synthesis of uncharged graphene in solution. Degradation of the molecules intercalated in GICs can be triggered by high temperature treatment or microwave irradiation, creating a gas pressure surge in graphite and exfoliation. Electrochemical exfoliation by applying a voltage in an electrolyte to a graphite electrode can be tuned by varying precursors, electrolytes and potential. Graphite electrodes can be either negatively or positively intercalated to obtain GICs that are subsequently exfoliated. We also discuss the materials that can be amenable to exfoliation, by employing a theoretical data-mining approach. The exfoliation of LMs usually results in a heterogeneous dispersion of flakes with different lateral size and thickness. This is a critical bottleneck for applications, and hinders the full exploitation of GRMs produced by solution processing. The establishment of procedures to control the morphological properties of exfoliated GRMs, which also need to be industrially scalable, is one of the key needs. Section III deals with the processing of flakes. (Ultra)centrifugation techniques have thus far been the most investigated to sort GRMs following ultrasonication, shear mixing, ball milling, microfluidization, and wet-jet milling. It allows sorting by size and thickness. Inks formulated from GRM dispersions can be printed using a number of processes, from inkjet to screen printing. Each technique has specific rheological requirements, as well as geometrical constraints. The solvent choice is critical, not only for the GRM stability, but also in terms of optimizing printing on different substrates, such as glass, Si, plastic, paper, etc, all with different surface energies. Chemical modifications of such substrates is also a key step. Sections IV-VII are devoted to the growth of GRMs on various substrates and their processing after growth to place them on the surface of choice for specific applications. The substrate for graphene growth is a key determinant of the nature and quality of the resultant film. The lattice mismatch between graphene and substrate influences the resulting crystallinity. Growth on insulators, such as SiO2, typically results in films with small crystallites, whereas growth on the close-packed surfaces of metals yields highly crystalline films. Section IV outlines the growth of graphene on SiC substrates. This satisfies the requirements for electronic applications, with well-defined graphene-substrate interface, low trapped impurities and no need for transfer. It also allows graphene structures and devices to be measured directly on the growth substrate. The flatness of the substrate results in graphene with minimal strain and ripples on large areas, allowing spectroscopies and surface science to be performed. We also discuss the surface engineering by intercalation of the resulting graphene, its integration with Si-wafers and the production of nanostructures with the desired shape, with no need for patterning. Section V deals with chemical vapour deposition (CVD) onto various transition metals and on insulators. Growth on Ni results in graphitized polycrystalline films. While the thickness of these films can be optimized by controlling the deposition parameters, such as the type of hydrocarbon precursor and temperature, it is difficult to attain single layer graphene (SLG) across large areas, owing to the simultaneous nucleation/growth and solution/precipitation mechanisms. The differing characteristics of polycrystalline Ni films facilitate the growth of graphitic layers at different rates, resulting in regions with differing numbers of graphitic layers. High-quality films can be grown on Cu. Cu is available in a variety of shapes and forms, such as foils, bulks, foams, thin films on other materials and powders, making it attractive for industrial production of large area graphene films. The push to use CVD graphene in applications has also triggered a research line for the direct growth on insulators. The quality of the resulting films is lower than possible to date on metals, but enough, in terms of transmittance and resistivity, for many applications as described in section V. Transfer technologies are the focus of section VI. CVD synthesis of graphene on metals and bottom up molecular approaches require SLG to be transferred to the final target substrates. To have technological impact, the advances in production of high-quality large-area CVD graphene must be commensurate with those on transfer and placement on the final substrates. This is a prerequisite for most applications, such as touch panels, anticorrosion coatings, transparent electrodes and gas sensors etc. New strategies have improved the transferred graphene quality, making CVD graphene a feasible option for CMOS foundries. Methods based on complete etching of the metal substrate in suitable etchants, typically iron chloride, ammonium persulfate, or hydrogen chloride although reliable, are time- and resource-consuming, with damage to graphene and production of metal and etchant residues. Electrochemical delamination in a low-concentration aqueous solution is an alternative. In this case metallic substrates can be reused. Dry transfer is less detrimental for the SLG quality, enabling a deterministic transfer. There is a large range of layered materials (LMs) beyond graphite. Only few of them have been already exfoliated and fully characterized. Section VII deals with the growth of some of these materials. Amongst them, h-BN, transition metal tri- and di-chalcogenides are of paramount importance. The growth of h-BN is at present considered essential for the development of graphene in (opto) electronic applications, as h-BN is ideal as capping layer or substrate. The interesting optical and electronic properties of TMDs also require the development of scalable methods for their production. Large scale growth using chemical/physical vapour deposition or thermal assisted conversion has been thus far limited to a small set, such as h-BN or some TMDs. Heterostructures could also be directly grown. Section VIII discusses advances in GRM functionalization. A broad range of organic molecules can be anchored to the sp(2) basal plane by reductive functionalization. Negatively charged graphene can be prepared in liquid phase (e.g. via intercalation chemistry or electrochemically) and can react with electrophiles. This can be achieved both in dispersion or on substrate. The functional groups of GO can be further derivatized. Graphene can also be noncovalently functionalized, in particular with polycyclic aromatic hydrocarbons that assemble on the sp(2) carbon network by pi-pi stacking. In the liquid phase, this can enhance the colloidal stability of SLG/FLG. Approaches to achieve noncovalent on-substrate functionalization are also discussed, which can chemically dope graphene. Research efforts to derivatize CNMs are also summarized, as well as novel routes to selectively address defect sites. In dispersion, edges are the most dominant defects and can be covalently modified. This enhances colloidal stability without modifying the graphene basal plane. Basal plane point defects can also be modified, passivated and healed in ultra-high vacuum. The decoration of graphene with metal nanoparticles (NPs) has also received considerable attention, as it allows to exploit synergistic effects between NPs and graphene. Decoration can be either achieved chemically or in the gas phase. All LMs,
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| 2. |
- Björk, Jonas, 1983-, et al.
(författare)
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The Role of Metal Adatoms in a Surface-Assisted Cyclodehydrogenation Reaction on a Gold Surface
- 2022
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Ingår i: Angewandte Chemie International Edition. - : Wiley-V C H Verlag GMBH. - 1433-7851 .- 1521-3773. ; 61:49
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Tidskriftsartikel (refereegranskat)abstract
- Dehydrogenation reactions are key steps in many metal-catalyzed chemical processes and in the on-surface synthesis of atomically precise nanomaterials. The principal role of the metal substrate in these reactions is undisputed, but the role of metal adatoms remains, to a large extent, unanswered, particularly on gold substrates. Here, we discuss their importance by studying the surface-assisted cyclodehydrogenation on Au(111) as an ideal model case. We choose a polymer theoretically predicted to give one of two cyclization products depending on the presence or absence of gold adatoms. Scanning probe microscopy experiments observe only the product associated with adatoms. We challenge the prevalent understanding of surface-assisted cyclodehydrogenation, unveiling the catalytic role of adatoms and their effect on regioselectivity. The study adds new perspectives to the understanding of metal catalysis and the design of on-surface synthesis protocols for novel carbon nanomaterials.
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| 3. |
- Gazzi, Arianna, et al.
(författare)
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Graphene, other carbon nanomaterials and the immune system: toward nanoimmunity-by-design
- 2020
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Ingår i: JPhys Materials. - : IOP Publishing. - 2515-7639. ; 3:3
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Tidskriftsartikel (refereegranskat)abstract
- Carbon-based materials (CBMs), such as graphene, nanodiamonds, carbon fibers, and carbon dots, have attracted a great deal scientific attention due to their potential as biomedical tools. Following exposure, particularly intravenous injection, these nanomaterials can be recognized by immune cells. Such interactions could be modulated by the different physicochemical properties of the materials (e.g. structure, size, and chemical functions), by either stimulating or suppressing the immune response. However, a harmonized cutting-edge approach for the classification of these materials based not only on their physicochemical parameters but also their immune properties has been missing. The European Commission-funded G-IMMUNOMICS and CARBO-IMmap projects aimed to fill this gap, developing a functional pipeline for the qualitative and quantitative immune characterization of graphene, graphene-related materials (GRMs), and other CBMs. The goal was to open breakthrough perspectives for the definition of the immune profiles of these materials. Here, we summarize our methodological approach, key results, and the necessary multidisciplinary expertise ranging across various fields, from material chemistry to engineering, immunology, toxicology, and systems biology. G-IMMUNOMICS, as a partnering project of the Graphene Flagship, the largest scientific research initiative on graphene worldwide, also complemented the studies performed in the Flagship on health and environmental impact of GRMs. Finally, we present the nanoimmunity-by-design concept, developed within the projects, which can be readily applied to other 2D materials. Overall, the G-IMMUNOMICS and CARBO-IMmap projects have provided new insights on the immune impact of GRMs and CBMs, thus laying the foundation for their safe use and future translation in medicine.
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| 4. |
- Huang, Xing, et al.
(författare)
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Semiconducting Conjugated Coordination Polymer with High Charge Mobility Enabled by "4+2" Phenyl Ligands
- 2023
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Ingår i: Journal of the American Chemical Society. - : AMER CHEMICAL SOC. - 0002-7863 .- 1520-5126. ; 145:4, s. 2430-2438
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Tidskriftsartikel (refereegranskat)abstract
- Electrically conductive coordination polymers and metal-organic frameworks are attractive emerging electroactive materials for (opto-)electronics. However, developing semiconducting coordination polymers with high charge carrier mobility for devices remains a major challenge, urgently requiring the rational design of ligands and topological networks with desired electronic structures. Herein, we demonstrate a strategy for synthesizing high-mobility semiconducting conjugated coordination polymers (c-CPs) utilizing novel conjugated ligands with D2h symmetry, namely, "4 + 2" phenyl ligands. Compared with the conventional phenyl ligands with C6h symmetry, the reduced symmetry of the "4 + 2" ligands leads to anisotropic coordination in the formation of c-CPs. Consequently, we successfully achieve a single-crystalline three-dimensional (3D) c-CP Cu4DHTTB (DHTTB = 2,5-dihydroxy-1,3,4,6-tetrathiolbenzene), containing orthogonal ribbon-like pi-d conjugated chains rather than 2D conjugated layers. DFT calculation suggests that the resulting Cu4DHTTB exhibits a small band gap (similar to 0.2 eV), strongly dispersive energy bands near the Fermi level with a low electron-hole reduced effective mass (similar to 0.2m0*). Furthermore, the four-probe method reveals a semiconducting behavior with a decent conductivity of 0.2 S/cm. Thermopower measurement suggests that it is a p-type semiconductor. Ultrafast terahertz photoconductivity measurements confirm Cu4DHTTB's semiconducting nature and demonstrate the Drude-type transport with high charge carrier mobilities up to 88 +/- 15 cm2 V-1 s-1, outperforming the conductive 3D coordination polymers reported till date. This molecular design strategy for constructing high-mobility semiconducting c-CPs lays the foundation for achieving high-performance c-CP-based (opto-)electronics.
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| 5. |
- Li, Guowei, et al.
(författare)
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Carbon-Tailored Semimetal MoP as an Efficient Hydrogen Evolution Electrocatalyst in Both Alkaline and Acid Media
- 2018
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Ingår i: Advanced Energy Materials. - : WILEY-V C H VERLAG GMBH. - 1614-6832 .- 1614-6840. ; 8:24
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Tidskriftsartikel (refereegranskat)abstract
- The electrolysis processes such as hydrogen evolution reaction (HER) require high efficient catalysts with robust surface stability. A high conductivity is also necessary to speed up the charge transport between the catalyst and the electrolyte. Recently, the observation of exceedingly high conductivity in the topological semimetal MoP, has provided a model catalyst to investigate the correlation between the electrical transport and the electrocatalytic activity for the HER. Thus, MoP is encapsulated in a Mo, P codoped carbon layer (MoP@C). This composite material exhibits outstanding HER performance, with an extremely low overpotential of 49 mV at a current density of 10 mA cm(-2) and a Tafel slope of 54 mV dec(-1) in an alkaline medium. In addition, electron transport analysis indicates that MoP exhibits high conductivity and mobility due to the existence of triple-point fermions and a complex Fermi surface. Furthermore, the presence of P-C and Mo-C bonds at the interface between the carbon layer and the MoP particles modulates the band structure of MoP@C and facilitates fast electron transfer, accumulation, and subsequent delocalization, which are in turn responsible for the excellent HER activity.
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| 6. |
- Li, Guowei, et al.
(författare)
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Dirac Nodal Arc Semimetal PtSn4: An Ideal Platform for Understanding Surface Properties and Catalysis for Hydrogen Evolution
- 2019
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Ingår i: Angewandte Chemie International Edition. - : WILEY-V C H VERLAG GMBH. - 1433-7851 .- 1521-3773.
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Tidskriftsartikel (refereegranskat)abstract
- Conductivity, carrier mobility, and a suitable Gibbs free energy are important criteria that determine the performance of catalysts for a hydrogen evolution reaction (HER). However, it is a challenge to combine these factors into a single compound. Herein, we discover a superior electrocatalyst for a HER in the recently identified Dirac nodal arc semimetal PtSn4. The determined turnover frequency (TOF) for each active site of PtSn4 is 1.54 H-2 s(-1) at 100 mV. This sets a benchmark for HER catalysis on Pt-based noble metals and earth-abundant metal catalysts. We make use of the robust surface states of PtSn4 as their electrons can be transferred to the adsorbed hydrogen atoms in the catalytic process more efficiently. In addition, PtSn4 displays excellent chemical and electrochemical stabilities after long-term exposure in air and long-time HER stability tests.
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| 7. |
- Li, Jiantong, 1980-, et al.
(författare)
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Scalable Fabrication and Integration of Graphene Microsupercapacitors through Full Inkjet Printing
- 2017
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Ingår i: ACS Nano. - : American Chemical Society (ACS). - 1936-0851 .- 1936-086X. ; 11:8, s. 8249-8256
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Tidskriftsartikel (refereegranskat)abstract
- A simple full-inkjet-printing technique is developed for the scalable fabrication of graphene-based microsupercapacitors (MSCs) on various substrates. High-performance graphene inks are formulated by integrating the electrochemically exfoliated graphene with a solvent exchange technique to reliably print graphene interdigitated electrodes with tunable geometry and "thickness. Along with the printed polyelectrolyte, poly(4-styrenesulfonic acid), the fully printed graphene-based MSCs attain the highest areal capacitance of similar to 0.7 mF/cm(2), substantially advancing the state-of-art of all-solid-state MSCs with printed graphene electrodes. The full printing solution enables scalable fabrication of MSCs and effective connection of them in parallel and/or in series at various scales. Remarkably, more than 100 devices have been connected to form large-scale MSC arrays as power banks on both silicon wafers and Kapton. Without any extra protection or encapsulation, the MSC arrays can be reliably charged up to 12 V and retain the performance even 8 months after fabrication.
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| 8. |
- Liu, Junzhi, et al.
(författare)
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Fused Dibenzo[a,m]rubicene : A New Bowl-Shaped Subunit of C-70 Containing Two Pentagons
- 2016
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Ingår i: Journal of the American Chemical Society. - : American Chemical Society (ACS). - 0002-7863 .- 1520-5126. ; 138:27, s. 8364-8367
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Tidskriftsartikel (refereegranskat)abstract
- Total synthetic approaches of fullerenes are the holy grail for organic chemistry. So far, the main attempts have focused on the synthesis of the buckmin-sterfullerene C-60. In contrast, access to subunits of the homologue C-70 remains challenging. Here, we demonstrate an efficient bottom-up strategy toward a novel bowl-shaped polycyclic aromatic hydrocarbons (PAH) C34 with two pentagons. This PAH represents a subunit for C-70 and of other higher fullerenes. The bowl-shaped structure was unambiguously determined by X-ray crystallography. A bowl-to-bowl inversion for a C-70 fragment in solution was investigated by dynamic NMR analysis, showing a bowl-to-bowl inversion energy (Delta G double dagger) of 16.7 kcal mol(-1), which is further corroborated by DFT calculations.
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| 9. |
- Lu, Yang, et al.
(författare)
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Precise tuning of interlayer electronic coupling in layered conductive metal-organic frameworks
- 2022
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Ingår i: Nature Communications. - : Nature Portfolio. - 2041-1723. ; 13:1
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Tidskriftsartikel (refereegranskat)abstract
- Layered metal-organic frameworks attract interests for optoelectronics and spintronics. Here, the authors report a strategy to tune interlayer charge transport and thermoelectric properties via side-chain induced control of the layer spacing. Two-dimensional conjugated metal-organic frameworks (2D c-MOFs) have attracted increasing interests for (opto)-electronics and spintronics. They generally consist of van der Waals stacked layers and exhibit layer-depended electronic properties. While considerable efforts have been made to regulate the charge transport within a layer, precise control of electronic coupling between layers has not yet been achieved. Herein, we report a strategy to precisely tune interlayer charge transport in 2D c-MOFs via side-chain induced control of the layer spacing. We design hexaiminotriindole ligands allowing programmed functionalization with tailored alkyl chains (HATI_CX, X = 1,3,4; X refers to the carbon numbers of the alkyl chains) for the synthesis of semiconducting Ni-3(HATI_CX)(2). The layer spacing of these MOFs can be precisely varied from 3.40 to 3.70 angstrom, leading to widened band gap, suppressed carrier mobilities, and significant improvement of the Seebeck coefficient. With this demonstration, we further achieve a record-high thermoelectric power factor of 68 +/- 3 nW m(-1) K-2 in Ni-3(HATI_C3)(2), superior to the reported holes-dominated MOFs.
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| 10. |
- Lu, Yang, et al.
(författare)
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sp-Carbon Incorporated Conductive Metal-Organic Framework as Photocathode for Photoelectrochemical Hydrogen Generation
- 2022
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Ingår i: Angewandte Chemie International Edition. - : Wiley. - 1433-7851 .- 1521-3773. ; 61:39
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Tidskriftsartikel (refereegranskat)abstract
- Metal-organic frameworks (MOFs) have attracted increasing interest for broad applications in catalysis and gas separation due to their high porosity. However, the insulating feature and the limited active sites hindered MOFs as photocathode active materials for application in photoelectrocatalytic hydrogen generation. Herein, we develop a layered conductive two-dimensional conjugated MOF (2D c-MOF) comprising sp-carbon active sites based on arylene-ethynylene macrocycle ligand via CuO4 linking, named as Cu3HHAE2. This sp-carbon 2D c-MOF displays apparent semiconducting behavior and broad light absorption till the near-infrared band (1600 nm). Due to the abundant acetylene units, the Cu3HHAE2 could act as the first case of MOF photocathode for photoelectrochemical (PEC) hydrogen generation and presents a record hydrogen-evolution photocurrent density of ≈260 μA cm−2 at 0 V vs. reversible hydrogen electrode among the structurally-defined cocatalyst-free organic photocathodes.
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