@phdthesis{Youk2022,
  author    = {Youk, Sol},
  title     = {Molecular design of heteroatom-doped nanoporous carbons with controlled porosity and surface polarity for gas physisorption and energy storage},
  doi       = {10.25932/publishup-53909},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-539098},
  school      = {Universit{\"a}t Potsdam},
  pages     = {145},
  year      = {2022},
  abstract  = {The world energy consumption has constantly increased every year due to economic development and population growth. This inevitably caused vast amount of CO2 emission, and the CO2 concentration in the atmosphere keeps increasing with economic growth. To reduce CO2 emission, various methods have been developed but there are still many bottlenecks to be solved. Solvents easily absorbing CO2 such as monoethanol-amine (MEA) and diethanolamine, for example, have limitations of solvent loss, amine degradation, vulnerability to heat and toxicity, and the high cost of regeneration which is especially caused due to chemisorption process. Though some of these drawbacks can be compensated through physisorption with zeolites and metal-organic frameworks (MOFs) by displaying significant adsorption selectivity and capacity even in ambient conditions, limitations for these materials still exist. Zeolites demand relatively high regeneration energy and have limited adsorption kinetics due to the exceptionally narrow pore structure. MOFs have low stability against heat and moisture and high manufacturing cost. Nanoporous carbons have recently received attention as an attractive functional porous material due to their unique properties. These materials are crucial in many applications of modern science and industry such as water and air purification, catalysis, gas separation, and energy storage/conversion due to their high chemical and thermal stability, and in particular electronic conductivity in combination with high specific surface areas. Nanoporous carbons can be used to adsorb environmental pollutants or small gas molecules such as CO2 and to power electrochemical energy storage devices such as batteries and fuel cells. In all fields, their pore structure or electrical properties can be modified depending on their purposes. This thesis provides an in-depth look at novel nanoporous carbons from the synthetic and the application point of view. The interplay between pore structure, atomic construction, and the adsorption properties of nanoporous carbon materials are investigated. Novel nanoporous carbon materials are synthesized by using simple precursor molecules containing heteroatoms through a facile templating method. The affinity, and in turn the adsorption capacity, of carbon materials toward polar gas molecules (CO2 and H2O) is enhanced by the modification of their chemical construction. It is also shown that these properties are important in electrochemical energy storage, here especially for supercapacitors with aqueous electrolytes which are basically based on the physisorption of ions on carbon surfaces. This shows that nanoporous carbons can be a "functional" material with specific physical or chemical interactions with guest species just like zeolites and MOFs. The synthesis of sp2-conjugated materials with high heteroatom content from a mixture of citrazinic acid and melamine in which heteroatoms are already bonded in specific motives is illustrated. By controlling the removal procedure of the salt-template and the condensation temperature, the role of salts in the formation of porosity and as coordination sites for the stabilization of heteroatoms is proven. A high amount of nitrogen of up to 20 wt. \%, oxygen contents of up to 19 wt.\%, and a high CO2/N2 selectivity with maximum CO2 uptake at 273 K of 5.31 mmol g-1 are achieved. Besides, the further controlled thermal condensation of precursor molecules and advanced functional properties on applications of the synthesized porous carbons are described. The materials have different porosity and atomic construction exhibiting a high nitrogen content up to 25 wt. \% as well as a high porosity with a specific surface area of more than 1800 m2 g-1, and a high performance in selective CO2 gas adsorption of 62.7. These pore structure as well as properties of surface affect to water adsorption with a remarkably high Qst of over 100 kJ mol-1 even higher than that of zeolites or CaCl2 well known as adsorbents. In addition to that, the pore structure of HAT-CN-derived carbon materials during condensation in vacuum is fundamentally understood which is essential to maximize the utilization of porous system in materials showing significant difference in their pore volume of 0.5 cm3 g-1 and 0.25 cm3 g-1 without and with vacuum, respectively. The molecular designs of heteroatom containing porous carbon derived from abundant and simple molecules are introduced in the presented thesis. Abundant precursors that already containing high amount of nitrogen or oxygen are beneficial to achieve enhanced interaction with adsorptives. The physical and chemical properties of these heteroatom-doped porous carbons are affected by mainly two parameters, that is, the porosity from the pore structure and the polarity from the atomic composition on the surface. In other words, controlling the porosity as well as the polarity of the carbon materials is studied to understand interactions with different guest species which is a fundamental knowledge for the utilization on various applications.},
  language  = {en}
}
@article{YanOschatzWu2020,
  author    = {Yan, Runyu and Oschatz, Martin and Wu, Feixiang},
  title     = {Towards stable lithium-sulfur battery cathodes by combining physical and chemical confinement of polysulfides in core-shell structured nitrogen-doped carbons},
  series = {Carbon},
  volume    = {161},
  journal   = {Carbon},
  publisher = {Elsevier Science},
  address   = {Amsterdam [u.a.]},
  issn      = {0008-6223},
  doi       = {10.1016/j.carbon.2020.01.046},
  pages     = {162 -- 168},
  year      = {2020},
  abstract  = {Despite intensive research on porous carbon materials as hosts for sulfur in lithium-sulfur battery cathodes, it remains a problem to restrain the soluble lithium polysulfide intermediates for a long-term cycling stability without the use of metallic or metal-containing species. Here, we report the synthesis of nitrogen-doped carbon materials with hierarchical pore architecture and a core-shell-type particle design including an ordered mesoporous carbon core and a polar microporous carbon shell. The initial discharge capacity with a sulfur loading up to 72 wt\% reaches over 900 mA h g(sulf)(ur)(-1) at a rate of C/2. Cycling performance measured at C/2 indicates similar to 90\% capacity retention over 250 cycles. In comparison to other carbon hosts, this architecture not only provides sufficient space for a high sulfur loading induced by the high-pore-volume particle core, but also enables a dual effect of physical and chemical confinement of the polysulfides to stabilize the cycle life by adsorbing the soluble intermediates in the polar microporous shell. This work elucidates a design principle for carbonaceous hosts that is capable to provide simultaneous physical-chemical confinement. This is necessary to overcome the shuttle effect towards stable lithium-sulfur battery cathodes, in the absence of additional membranes or inactive metal-based anchoring materials.},
  language  = {en}
}
@article{QinHeilSchmidtetal.2019,
  author    = {Qin, Qing and Heil, T. and Schmidt, J. and Schmallegger, Max and Gescheidt, Georg and Antonietti, Markus and Oschatz, Martin},
  title     = {Electrochemical Fixation of Nitrogen and Its Coupling with Biomass Valorization with a Strongly Adsorbing and Defect Optimized Boron-Carbon-Nitrogen Catalyst},
  series = {ACS Applied Energy Materials},
  volume    = {2},
  journal   = {ACS Applied Energy Materials},
  number    = {11},
  publisher = {American Chemical Society},
  address   = {Washington},
  issn      = {2574-0962},
  doi       = {10.1021/acsaem.9b01852},
  pages     = {8359 -- 8365},
  year      = {2019},
  abstract  = {The electrochemical conversion of low-cost precursors into high-value chemicals using renewably generated electricity is a promising approach to build up an environmentally friendly energy cycle, including a storage element. The large-scale implementation of such process can, however, only be realized by the design of cost-effective electrocatalysts with high efficiency and highest stability. Here, we report the synthesis of N and B codoped porous carbons. The constructed B-N motives combine abundant unpaired electrons and frustrated Lewis pairs (FLPs). They result in desirable performance for electrochemical N-2 reduction reaction (NRR) and electrooxidation of 5-hydroxymethylfurfural (HMF) in the absence of any metal cocatalyst. A maximum Faradaic efficiency of 15.2\% with a stable NH3 production rate of 21.3 mu g h(-1) mg(-1) is obtained in NRR. Besides, 2,5-furandicarboxylic acid (FDCA) is first obtained by using non-metalbased electrocatalysts at a conversion of 71\% and with yield of 57\%. Gas adsorption experiments elucidate the relationship between the structure and the ability of the catalysts to activate the substrate molecules. This work opens up deep insights for the rational design of non-metal-based catalysts for potential electrocatalytic applications and the possible enhancement of their activity by the introduction of FLPs and point defects at grain boundaries.},
  language  = {en}
}
@article{PerovicZeiningerOschatz2020,
  author    = {Perovic, Milena and Zeininger, Lukas and Oschatz, Martin},
  title     = {Immobilization of gold-on-carbon catalysts onto perfluorocarbon emulsion droplets to promote oxygen delivery in aqueous phase (D)-glucose oxidation},
  series = {ChemCatChem},
  volume    = {13},
  journal   = {ChemCatChem},
  number    = {1},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {1867-3880},
  doi       = {10.1002/cctc.202001590},
  pages     = {196 -- 201},
  year      = {2020},
  abstract  = {The catalytic activity of metal nanoparticles (NPs) supported on porous supports can be controlled by various factors, such as NPs size, shape, or dispersivity, as well as their interaction with the support or the properties of the support material itself. However, these intrinsic properties are not solely responsible for the catalytic behavior of the overall reaction system, as the local environment and surface coverage of the catalyst with reactants, products, intermediates and other invloved species often play a crucial role in catalytic processes as well. Their contribution can be particularly critical in liquid-phase reactions with gaseous reactants that often suffer from low solubiltiy. One example is (D)-glucose oxidation with molecular oxygen over gold nanoparticles supported on porous carbons. The possibility to promote oxygen delivery in such aqueous phase oxidation reactions via the immobilization of heterogenous catalysts onto the interface of perfluorocarbon emulsion droplets is reported here. Gold-on-carbon catalyst particles can stabilize perfluorocarbon droplets in the aqueous phase and the local concentration of the oxidant in the surroundings of the gold nanoparticles accelerates the rate-limiting step of the reaction. Consequently, the reaction rate of a system with the optimal volume fraction of fluorocarbon is higher than a reference emulsion system without fluorocarbon, and the effect is observed even without additional oxygen supply.},
  language  = {en}
}
@misc{PerovicZeiningerOschatz2020,
  author    = {Perovic, Milena and Zeininger, Lukas and Oschatz, Martin},
  title     = {Immobilization of gold-on-carbon catalysts onto perfluorocarbon emulsion droplets to promote oxygen delivery in aqueous phase (D)-glucose oxidation},
  series = {Zweitver{\"o}ffentlichungen der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  journal   = {Zweitver{\"o}ffentlichungen der Universit{\"a}t Potsdam : Mathematisch-Naturwissenschaftliche Reihe},
  number    = {1},
  issn      = {1867-3880},
  doi       = {10.25932/publishup-56947},
  url       = {http://nbn-resolving.de/urn:nbn:de:kobv:517-opus4-569471},
  pages     = {8},
  year      = {2020},
  abstract  = {The catalytic activity of metal nanoparticles (NPs) supported on porous supports can be controlled by various factors, such as NPs size, shape, or dispersivity, as well as their interaction with the support or the properties of the support material itself. However, these intrinsic properties are not solely responsible for the catalytic behavior of the overall reaction system, as the local environment and surface coverage of the catalyst with reactants, products, intermediates and other invloved species often play a crucial role in catalytic processes as well. Their contribution can be particularly critical in liquid-phase reactions with gaseous reactants that often suffer from low solubiltiy. One example is (D)-glucose oxidation with molecular oxygen over gold nanoparticles supported on porous carbons. The possibility to promote oxygen delivery in such aqueous phase oxidation reactions via the immobilization of heterogenous catalysts onto the interface of perfluorocarbon emulsion droplets is reported here. Gold-on-carbon catalyst particles can stabilize perfluorocarbon droplets in the aqueous phase and the local concentration of the oxidant in the surroundings of the gold nanoparticles accelerates the rate-limiting step of the reaction. Consequently, the reaction rate of a system with the optimal volume fraction of fluorocarbon is higher than a reference emulsion system without fluorocarbon, and the effect is observed even without additional oxygen supply.},
  language  = {en}
}
@article{HwangZhangYouketal.2021,
  author    = {Hwang, Jinyeon and Zhang, Wuyong and Youk, Sol and Schutjajew, Konstantin and Oschatz, Martin},
  title     = {Understanding structure-property relationships under experimental conditions for the optimization of lithium-ion capacitor anodes based on all-carbon-composite materials},
  series = {Energy technology : generation, conversion, storage, distribution},
  volume    = {9},
  journal   = {Energy technology : generation, conversion, storage, distribution},
  number    = {3},
  publisher = {Wiley-VCH},
  address   = {Weinheim},
  issn      = {2194-4296},
  doi       = {10.1002/ente.202001054},
  pages     = {8},
  year      = {2021},
  abstract  = {The nanoscale combination of a conductive carbon and a carbon-based material with abundant heteroatoms for battery electrodes is a method to overcome the limitation that the latter has high affinity to alkali metal ions but low electronic conductivity. The synthetic protocol and the individual ratios and structures are important aspects influencing the properties of such multifunctional compounds. Their interplay is, herein, investigated by infiltration of a porous ZnO-templated carbon (ZTC) with nitrogen-rich carbon obtained by condensation of hexaazatriphenylene-hexacarbonitrile (HAT-CN) at 550-1000 degrees C. The density of lithiophilic sites can be controlled by HAT-CN content and condensation temperature. Lithium storage properties are significantly improved in comparison with those of the individual compounds and their physical mixtures. Depending on the uniformity of the formed composite, loading ratio and condensation temperature have different influence. Most stable operation at high capacity per used monomer is achieved with a slowly dried composite with an HAT-CN:ZTC mass ratio of 4:1, condensed at 550 degrees C, providing more than 400 mAh g(-1) discharge capacity at 0.1 A g(-1) and a capacity retention of 72\% after 100 cycles of operation at 0.5 A g(-1) due to the homogeneity of the composite and high content of lithiophilic sites.},
  language  = {en}
}