Does boron or nitrogen substitution affect hydrogen physisorption on open carbon surfaces?

Incorporation of heteroatoms in carbon materials is commonly expected to influence their physical or chemical properties. However, contrary to previous results for methane adsorption, no technologically significant effect was identified for the hydrogen physisorption energies (measured 4.1-4.6 kJ mol-1 and calculated qst = -ΔHads = 4.1 ± 0.7 kJ mol-1 using a comprehensive set of levels of theory) as a function of B- and N-substitution of a mid-plane C-site on open carbon surfaces.

Effects of lignin syringyl to guaiacyl ratio on cottonwood biochar adsorbent properties and performance.

Lignin syringyl to guaiacyl ratio (S/G) has long been suspected to have measurable impacts on biochar formation, but these effects are challenging to observe in biochars formed from whole biomass. When the model bioenergy feedstock Populus trichocarpa (cottonwood), with predictable lignin macromolecular structure tied to genetic variation, is used as feedstock for biochar production, these effects become visible. In this work, two P. trichocarpa variants having lignin S/G of 1.67 and 3.88 were ground and pyrolyzed at 700 °C. Water-demineralization of feedstock was used to simultaneously evaluate any synergistic influences of S/G and naturally-occurring potassium on biochar physicochemical properties and performance. The strongest effects of lignin S/G were observed on specific surface area (SBET) and oxygen-content, with S/G of 1.67 improving SBET by 11% and S/G of 3.88 increasing total oxygen content in demineralized biochars. Functional performance was evaluated by breakthrough testing in 1% NH3. Breakthrough times for biochars were nearly double that of a highly microporous activated carbon reference material, and biochar with S/G of 3.88 had 10% longer breakthrough time than its lower S/G corollary. Results support a combination of pore structure and oxygen-functionalities in controlling ammonia breakthrough for biochar.

Hydrogen Adsorption in Ultramicroporous Metal-Organic Frameworks Featuring Silent Open Metal Sites.

In this study, we utilized an ultramicroporous metal-organic framework (MOF) named [Ni3(pzdc)2(ade)2(H2O)4]·2.18H2O (where H3pzdc represents pyrazole-3,5-dicarboxylic acid and ade represents adenine) for hydrogen (H2) adsorption. Upon activation, [Ni3(pzdc)2(ade)2] was obtained, and in situ carbon monoxide loading by transmission infrared spectroscopy revealed the generation of open Ni(II) sites. The MOF displayed a Brunauer-Emmett-Teller (BET) surface area of 160 m2/g and a pore size of 0.67 nm. Hydrogen adsorption measurements conducted on this MOF at 77 K showed a steep increase in uptake (up to 1.93 mmol/g at 0.04 bar) at low pressure, reaching a H2 uptake saturation at 2.11 mmol/g at ∼0.15 bar. The affinity of this MOF for H2 was determined to be 9.7 ± 1.0 kJ/mol. In situ H2 loading experiments supported by molecular simulations confirmed that H2 does not bind to the open Ni(II) sites of [Ni3(pzdc)2(ade)2], and the high affinity of the MOF for H2 is attributed to the interplay of pore size, shape, and functionality.