“Salt Templating”: A Simple and Sustainable Pathway toward Highly Porous Functional Carbons from Ionic Liquids

Fechler, Nina; Fellinger, Tim‐Patrick; Antonietti, Markus

doi:10.1002/adma.201203422

Cited by 472 publications

(381 citation statements)

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“…8388 A salt-templating method was introduced to obtain micro-as well as mesoporosity in NdCs by a simple one-step process. 89 In this method, the pore structures and specific surface areas are tuned by just changing the type of salts and salt concentrations. As a result, a variety of NdC and codoped carbons with very high specific surface areas up to 3600 m 2 g ¹1 were obtained.…”

Section: Nanoarchitectonics Of Functional Carbons Using Ils/pils and mentioning

confidence: 99%

Carbon- and Nitrogen-Based Porous Solids: A Recently Emerging Class of Materials

Sakaushi

Antonietti

2014

Bulletin of the Chemical Society of Japan

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118

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In this account, the emergence of a new family of porous solid-state materials based on carbon and nitrogen is discussed. This started with the observation that carbon nitride, a polymeric material with a composition close to C 3 N 4 , is not only unexpectedly thermally and chemically stable, but a semiconductor at the same time and able to catalyze a variety of chemical reactions, such as DielsAlder cyclizations, oxidations, and photochemical water splitting. Carbon nitride is however already sufficiently reviewed but related materials with similar potential have essentially been not sufficiently covered. The remaining structures are manifold and cover the range from on the one hand covalent triazine frameworks (CTFs) as new semiconducting porous solid-state materials to the other porous nitrogen-doped carbons (NdCs) as catalysts which are known to be applicable in a variety of electrocatalytic reactions. CTFs are porous polymeric frameworks constituted of triazine rings and other aromatic rings. Chemical binding motifs and crystal structures can be used to control the band structure of such an (organic) solid-state material. Porous NdCs are usually made by adding nitrogen sources to classical carbonization recipes, and they are attracting a lot of interest because of their catalytic activity for electrochemical processes, such as oxygen reduction reaction (ORR). This account will summarize state-ofthe-art work on those systems being next-generation catalysts for different kinds of reactions, which are affordable and high-performance catalysts with unique principle for emergence of catalytic activities, combining theoretical and experimental studies together with basic and applied science in a range of scientific fields from chemistry to physics. Indeed, the first exploration of the above materials as candidates for components of fuel cells and rechargeable metalair batteries are discussed.

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Section: Nanoarchitectonics Of Functional Carbons Using Ils/pils and mentioning

confidence: 99%

Carbon- and Nitrogen-Based Porous Solids: A Recently Emerging Class of Materials

Sakaushi

Antonietti

2014

Bulletin of the Chemical Society of Japan

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118

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“…IL based syntheses of carbon materials have been established in manifold ways in recent years of research. [1][2][3][4][5][6][7][21][22][23][39][40][41][42][43][44][45][46][47][48] Especially liquid salts with dicyanamide anions are a powerful precursor for N-doped carbons, [1][2][3][4][5][6][7] and for advanced co-doping with S. 27 Herein we present a modified IL route using phosphonium additives, paving the way towards P-and N-co-doped carbonsa class of materials only rarely reported in the literature so far. 36 BMP-dca with 40 mol% of tetrabutyl-phosphonium-bromide (TBuPBr) as a phosphorus source was therefore carbonised at 1000 1C in a constant flow of inert gas (see ESI † for details).…”

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confidence: 99%

Nitrogen- and phosphorus-co-doped carbons with tunable enhanced surface areas promoted by the doping additives

et al. 2013

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Herein we present a modified IL route using phosphonium additives, paving the way towards P-and N-co-doped carbonsa class of materials only rarely reported in the literature so far. 36BMP-dca with 40 mol% of tetrabutyl-phosphonium-bromide (TBuPBr) as a phosphorus source was therefore carbonised at 1000 1C in a constant flow of inert gas (see ESI † for details). The black solid product is a carbonaceous material exhibiting a local graphitic order that is limited in its extension. This can be derived from the powder X-ray diffraction (PXRD) patterns showing broadened, but intense, (002) and (100) reflexes typical for a stacking motif in turbostratic-like carbons (compare Fig. S1, ESI †). The black product was also characterised by means of elemental combustion analysis (EA) and inductively coupled plasma optical emission spectrometry (ICP-OES) to determine the degree of heteroatom-doping: 4.1 wt% of N-doping (EA) and 5.7 wt% of P-doping (ICP-OES) are revealed. The material is thus successfully dually doped; especially the remarkably high degree of P-doping compared to other approaches 36-38 is noteworthy and points out the advantages of the method. To also prove the homogeneity of the material, elemental mapping based on energy dispersive X-ray spectroscopy (EDX) and wavelength dispersive X-ray spectroscopy (WDX) was performed. The data are provided in the ESI † (Fig. S2-S5, ESI †), showing clearly that the dopants are spread homogeneously throughout the material. Significant local concentration maxima cannot be found. The binding environments of both N and P could be elucidated by X-ray photoelectron spectroscopy (XPS), and the detailed N1s and P2p scans are depicted in Fig. 1. The results for nitrogen are as expected according to our previous studies:1,2,27,46 three deconvolved contributions appear at 398.13 eV, 400.88 eV and 402.80 eV that can be assigned to pyridinic and pyrollic nitrogen species, quaternary graphitic nitrogen and minor oxidised nitrogen binding motifs (due to oxidative processes on the surface of the materials), respectively. 16,34,49,50 The N doping thus occurs with N atoms firmly bound to the carbon backbone. To clearly assign the P2p XPS scan to certain chemical environments is however more difficult. Fig. 1 Deconvolved XPS scans of the N1s and P2p orbitals of the material.

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“…Fechler et al has examined the carbonization of different ionic liquid precursors containing heteroatoms like B, N in the salt melt of ZnCl 2 /ACl (A: Li, Na, K) at temperatures up to 1400 C. 67 In these systems, the precursors can be completely solvated by the salt melt, thus enabling the formation of a homogeneous solution phase, for which porous carbon precipitates as a result of heating to high temperature by phase separation (Figure 9). The products with an irregular morphology demonstrate SSA of up to 2000 m 2 g −1 and porosity of up to 2.75 cm 3 g −1 .…”

Section: 70mentioning

confidence: 99%

Ionothermal Synthesis of Carbon Nanostructures: Playing with Carbon Chemistry in Inorganic Salt Melt

Liu¹

2016

Nano Adv

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Citation: X. Liu, Nano Adv., 2016, 1, 90−103. Solution growth of sp2 carbon nanostructures from molecular precursors has been a tremendous challenge as the operation temperature windows offered by most solvents used in wet chemistry synthesis are too low to allow the complete condensation and carbonization of normal simple molecules, such as sugar. Inorganic ionic salt melt has recently enabled direct solution growth of carbon nanostructures with tailored heteroatom doping and porosity, which are indispensable for most functionalities of carbon materials. Compared with molecular solvents (i.e., water and most organic solvents), the ionic salt melt not only provides a wider and higher operation temperature window, but also strong solvation power that ensures the carbonization and precipitation in a controllable manner. Starting from molecules like sugar, this ionothermal process can produce disordered carbon, graphene-like two-dimensional carbon, highly porous carbon nanosheets, etc., depending on the synthetic conditions. Doping of heteroatoms, such as nitrogen, into the resultant carbon can be made by using oxysalt additives such as nitrate, in which N atoms are reduced and finally incorporated into the sp 2 carbon network. The ionothermal process also can produce nanostructured carbon in a templated fashion in which both salt particles and molecular precursors can serve as the hard or soft template. Due to the favorable microstructure and chemical composition, the ionothermal-derived carbon nanostructures have found diverse applications, as exemplified here by electrocatalysis for oxygen reduction and capacitive energy storage. Further development in ionothermal process will focus on the scalable, green production of carbon nanostructures orientated for commercial applications.

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“Salt Templating”: A Simple and Sustainable Pathway toward Highly Porous Functional Carbons from Ionic Liquids

Cited by 472 publications

References 32 publications

Carbon- and Nitrogen-Based Porous Solids: A Recently Emerging Class of Materials

Carbon- and Nitrogen-Based Porous Solids: A Recently Emerging Class of Materials

Nitrogen- and phosphorus-co-doped carbons with tunable enhanced surface areas promoted by the doping additives

Ionothermal Synthesis of Carbon Nanostructures: Playing with Carbon Chemistry in Inorganic Salt Melt

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