skip to main content

Title: Synopsis of Factors Affecting Hydrogen Storage in Biomass-Derived Activated Carbons
Hydrogen (H2) is largely regarded as a potential cost-efficient clean fuel primarily due to its beneficial properties, such as its high energy content and sustainability. With the rising demand for H2 in the past decades and its favorable characteristics as an energy carrier, the escalating USA consumption of pure H2 can be projected to reach 63 million tons by 2050. Despite the tremendous potential of H2 generation and its widespread application, transportation and storage of H2 have remained the major challenges of a sustainable H2 economy. Various efforts have been undertaken by storing H2 in activated carbons, metal organic frameworks (MOFs), covalent organic frameworks (COFs), etc. Recently, the literature has been stressing the need to develop biomass-based activated carbons as an effective H2 storage material, as these are inexpensive adsorbents with tunable chemical, mechanical, and morphological properties. This article reviews the current research trends and perspectives on the role of various properties of biomass-based activated carbons on its H2 uptake capacity. The critical aspects of the governing factors of H2 storage, namely, the surface morphology (specific surface area, pore volume, and pore size distribution), surface functionality (heteroatom and functional groups), physical condition of H2 storage (temperature and pressure), and thermodynamic more » properties (heat of adsorption and desorption), are discussed. A comprehensive survey of the literature showed that an “ideal” biomass-based activated carbon sorbent with a micropore size typically below 10 Å, micropore volume greater than 1.5 cm3/g, and high surface area of 4000 m2/g or more may help in substantial gravimetric H2 uptake of >10 wt% at cryogenic conditions (−196 °C), as smaller pores benefit by stronger physisorption due to the high heat of adsorption. « less
Authors:
; ;
Award ID(s):
2123495
Publication Date:
NSF-PAR ID:
10302957
Journal Name:
Sustainability
Volume:
13
Issue:
4
ISSN:
2071-1050
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract
    Excessive phosphorus (P) applications to croplands can contribute to eutrophication of surface waters through surface runoff and subsurface (leaching) losses. We analyzed leaching losses of total dissolved P (TDP) from no-till corn, hybrid poplar (Populus nigra X P. maximowiczii), switchgrass (Panicum virgatum), miscanthus (Miscanthus giganteus), native grasses, and restored prairie, all planted in 2008 on former cropland in Michigan, USA. All crops except corn (13 kg P ha−1 year−1) were grown without P fertilization. Biomass was harvested at the end of each growing season except for poplar. Soil water at 1.2 m depth was sampled weekly to biweekly for TDP determination during March–November 2009–2016More>>
  2. Abstract Biochar is a solid by-product of thermochemical conversion of biomass to bio-oil and syngas. It has a carbonaceous skeleton, a small amount of heteroatom functional groups, mineral matter, and water. Biochar’s unique physicochemical structures lead to many valuable properties of important technological applications, including its sorption capacity. Indeed, biochar’s wide range of applications include carbon sequestration, reduction in greenhouse gas emissions, waste management, renewable energy generation, soil amendment, and environmental remediation. Aside from these applications, new scientific insights and technological concepts have continued to emerge in the last decade. Consequently, a systematic update of current knowledge regarding the complexmore »nature of biochar, the scientific and technological impacts, and operational costs of different activation strategies are highly desirable for transforming biochar applications into industrial scales. This communication presents a comprehensive review of physical activation/modification strategies and their effects on the physicochemical properties of biochar and its applications in environment-related fields. Physical activation applied to the activation of biochar is discussed under three different categories: I) gaseous modification by steam, carbon dioxide, air, or ozone; II) thermal modification by conventional heating and microwave irradiation; and III) recently developed modification methods using ultrasound waves, plasma, and electrochemical methods. The activation results are discussed in terms of different physicochemical properties of biochar, such as surface area; micropore, mesopore, and total pore volume; surface functionality; burn-off; ash content; organic compound content; polarity; and aromaticity index. Due to the rapid increase in the application of biochar as adsorbents, the synergistic and antagonistic effects of activation processes on the desired application are also covered.« less
  3. In this study, we systematically investigated the effects of thermal air oxidation on the properties of biomass-derived BC made at carbonization temperatures (HTTs) of 300–700 ˚C. BC produced by including air in the carbonization step was found to have a low surface area and underdeveloped pore structure. Substantial changes of BC were observed after post-pyrolysis thermal air oxidation (PPAO). Well-carbonized BC samples made anoxically at relatively high HTTs (600 and 700 ˚C) showed, after PPAO, significant increases in N2 BET surface area (SA) (up to 700 times), porosity (< 60 Å) (up to 95 times), and adsorptivity (up to 120more »times) of neutral organic species including two triazine herbicides and one natural estrogen. Partially carbonized BC made at a lower HTT (300 or 400 ˚C) showed moderate increases in these properties after PPAO, but a large increase in the intensity of Fourier transform infrared spectroscopy bands corresponding to various oxygen-containing functional groups. Well-carbonized BC samples, on the other hand, were deficient in surface oxygen functionality even after the PPAO treatment. Adsorption of the test organic compounds on BC generally trended with BET SA when it was less than 300 m2/g, but BET SA was poorly predictive of adsorption when it was greater than 300 m2/g. Overall, our results suggest that thermal reactions between molecular oxygen and BC 1) increase surface oxygen functionality more effectively for low-HTT than for high-HTT BC samples; 2) increase SA and porosity (< 60 Å) especially for high-HTT BC samples; and 3) create new adsorption sites and/or relieve steric restriction of organic molecules to micropores, thereby enhancing the adsorptivity of BC. These results will prove useful not only for understanding the fate of environmental BC but also in devising strategies for improving the practical performance of the engineered form of BC (i.e., biochar).« less
  4. A series of N-doped porous carbons with different textural properties and N contents was prepared from a mixture of algae and glucose and their capability for the separation of CO 2 /CH 4 , C 2 H 6 /CH 4 , and CO 2 /H 2 binary mixtures under different conditions (bulk pressure, mixture composition, and temperature) were subsequently assessed in great detail. It was observed that the gas (C 2 H 6 , CO 2 , CH 4 , and H 2 ) adsorption capacity at different pressure regions was primarily governed by different adsorbent parameters (N level, narrowmore »micropore volume, and BET specific surface area). More interestingly, it was found that N-doping can selectively enhance the heats of adsorption of C 2 H 6 and CO 2 , while it had a negligible effect on those of CH 4 and H 2 . The adsorption equilibrium selectivities for separating C 2 H 6 /CH 4 , CO 2 /CH 4 , and CO 2 /H 2 gas mixture pairs on the porous carbons were predicted using the ideal adsorbed solution theory (IAST) based on pure-component adsorption isotherms. In particular, sample NAHA-1 exhibited by far the best performance (in terms of gas adsorption capacity and selectivity) reported for porous carbons for the separation of these three binary mixtures. More significantly, NAHA-1 carbon outperforms many of its counterparts ( e.g. MOFs and zeolites), emphasizing the important role of carbonaceous adsorbents in gas purification and separation.« less
  5. It is urgent to enhance battery energy storage capability to satisfy the increasing energy demand in modern society and reduce the average energy capacity cost. Among the candidates for next-generation high energy storage systems, the lithium-sulfur battery is especially attractive because of its high theoretical specific energy (around 2600 W h kg-1) and cost savings potential.1 In addition to the high theoretical capacity of sulfur cathode as high as 1,673 mA h g-1, sulfur is further appealing due to its abundance in nature, low cost, and low toxicity. Despite these advantages, the application of sulfur cathodes to date has beenmore »hindered by a number of obstacles, including low active material loading, low electronic conductivity, shuttle effects, and sluggish sulfur conversion kinetics.2 The traditional 2D planer thick electrode is considered as a general approach to enhance the mass loading of the lithium-sulfur (Li-S) battery.3 However, the longer diffusion length of lithium ions required in the thick electrode decrease the wettability of the electrolyte (into the entire cathode) and utilization ratio of active materials.4 Encapsulating active sulfur in carbon hosts is another common method to improve the performance of sulfur cathodes by enhancing the electronic conductivity and restricting shuttle effects. Nevertheless, it is also reported that the encapsulation approach causes unfavorable carbon agglomeration with low dimensional carbons and a low energy density of the battery with high dimensional carbons. Although an effort to induce defects in the cathode was made to promote sulfur conversion kinetic conditions, only one type of defect has demonstrated limited performance due to the strong adsorption of the uncatalyzed clusters to the defects (i.e.: catalyst poisoning). 5 To mitigate the issues listed above, herein we propose a novel sulfur electrode design strategy enabled by additive manufacturing and oxidative chemical vapor deposition (oCVD).6,7 Specifically, the electrode is designed to have a hierarchal hollow structure via a stereolithography technique to increase sulfur usage. Microchannels are constructed on the tailored sulfur cathode to further fortify the wettability of the electrolyte. The as-printed cathode is then sintered at 700 °C in a reducing atmosphere (e.g.: H2) in order to generate a carbon skeleton (i.e.: carbonization of resin) with intrinsic carbon defects. A cathode treatment with benzene sulfonic acid further induces additional defects (non-intrinsic) to enhance the sulfur conversion kinetic. Furthermore, intrinsic defects engineering is expected to synergistically create favorable sulfur conversion conditions and mitigate the catalyst poisoning issue. In this study, the oCVD technique is leveraged to produce a conformal coating layer to eliminate shuttle effects, unfavored in the Li-S battery performance. Identified by SEM and TEM characterizations, the oCVD PEDOT is not only covered on the surface of the cathode but also the inner surface of the microchannels. High resolution x-ray photoelectron spectroscopy analyses (C 1s and S 2p orbitals) between pristine and modified sample demonstrate that the high concentration of the defects have been produced on the sulfur matrix after sintering and posttreatment. In-operando XRD diffractograms show that the Li2S is generated in the oCVD PEDOT-coated sample during the charge and discharge process even with a high current density, confirming an eminent sulfur conversion kinetic condition. In addition, ICP-OES results of lithium metal anode at different states of charge (SoC) verify that the shuttle effects are excellently restricted by oCVD PEDOT. Overall, the high mass loading (> 5 mg cm-2) with elevated sulfur utilization ratio, accelerated reaction kinetics, and stabilized electrochemical process have been achieved on the sulfur cathode by implementing this innovative cathode design strategy. The results of this study demonstrate significant promises of employing pure sulfur powder with high electrochemical performance and suggest a pathway to the higher energy and power density battery.« less