Fast and Slow Rates of Naphthalene Sorption to Biochars Produced at Different Temperatures

This study investigated the sorption kinetics of a model solute (naphthalene) with a series of biochars prepared from a pine wood at 150–700 °C (referred as PW100–PW700) to probe the effect of the degree of carbonization of a biochar. The samples were characterized by the elemental compositions, thermal gravimetric analyses, Fourier transform IR spectroscopy, scanning electron microscopy, Brunauer–Emmett–Teller-N₂ surface areas (SA), and pore size distributions. Naphthalene exhibited a fast rate of sorption to PW150 owning a high oxygen content and a small SA, due supposedly to the solute partition into a swollen well-hydrated uncarbonized organic matter of PW150. The partial removal of polar-group contents in PW250/PW350, which increased the compactness of the partition medium, decreased the diffusion of the solute into the partition phase to result in a slow sorption rate. With PW500 and PW700 displaying low oxygen contents and high SA, the solute sorption rates were fast, attributed to the near exhaustion of a partition phase in the sample and to the fast solute adsorption on the carbonized biochar component. The results illustrate that the sorption rate of a solute with biochars is controlled largely by the solute’s diffusivity in the biochar’s partition phase, in which the medium compactness affects directly the solute diffusivity

Adsorption of Polycyclic Aromatic Hydrocarbons by Graphene and Graphene Oxide Nanosheets

The adsorption of naphthalene, phenanthrene, and pyrene onto graphene (GNS) and graphene oxide (GO) nanosheets was investigated to probe the potential adsorptive sites and molecular mechanisms. The microstructure and morphology of GNS and GO were characterized by elemental analysis, XPS, FTIR, Raman, SEM, and TEM. Graphene displayed high affinity to the polycyclic aromatic hydrocarbons (PAHs), whereas GO adsorption was significantly reduced after oxygen-containing groups were attached to GNS surfaces. An unexpected peak was found in the curve of adsorption coefficients (<i>K</i>_d) with the PAH equilibrium concentrations. The hydrophobic properties and molecular sizes of the PAHs affected the adsorption of G and GO. The high affinities of the PAHs to GNS are dominated by π–π interactions to the flat surface and the sieving effect of the powerful groove regions formed by wrinkles on GNS surfaces. In contrast, the adsorptive sites of GO changed to the carboxyl groups attaching to the edges of GO because the groove regions disappeared and the polar nanosheet surfaces limited the π–π interactions. The TEM and SEM images initially revealed that after loading with PAH, the conformation and aggregation of GNS and GO nanosheets dramatically changed, which explained the observations that the potential adsorption sites of GNS and GO were unusually altered during the adsorption process

Quantification of Chemical States, Dissociation Constants and Contents of Oxygen-containing Groups on the Surface of Biochars Produced at Different Temperatures

Surface functional groups such as carboxyl play a vital role in the environmental applications of biochar as a soil amendment. However, the quantification of oxygen-containing groups on a biochar surface still lacks systematical investigation. In this paper, we report an integrated method combining chemical and spectroscopic techniques that were established to quantitatively identify the chemical states, dissociation constants (p<i>K</i>_a), and contents of oxygen-containing groups on dairy manure-derived biochars prepared at 100–700 °C. Unexpectedly, the dissociation pH of carboxyl groups on the biochar surface covered a wide range of pH values (pH 2–11), due to the varied structural microenvironments and chemical states. For low temperature biochars (≤350 °C), carboxyl existed not only as hydrogen-bonded carboxyl and unbonded carboxyl groups but also formed esters at the surface of biochars. The esters consumed OH^– via saponification in the alkaline pH region and enhanced the dissolution of organic matter from biochars. For high temperature biochars (≥500 °C), esters came from carboxyl were almost eliminated via carbonization (ester pyrolysis), while lactones were developed. The surface density of carboxyl groups on biochars decreased sharply with the increase of the biochar-producing temperature, but the total contents of the surface carboxyls for different biochars were comparable (with a difference <3-fold) as a result of the expanded surface area at high pyrolytic temperatures. Understanding the wide p<i>K</i>_a ranges and the abundant contents of carboxyl groups on biochars is a prerequisite to recognition of the multifunctional applications and biogeochemical cycling of biochars

Bisolute Sorption and Thermodynamic Behavior of Organic Pollutants to Biomass-derived Biochars at Two Pyrolytic Temperatures

The bisolute sorption and thermodynamic behavior of organic pollutants on low temperature biochars (LTB) at 300 °C and high temperature biochars (HTB) at 700 °C were determined to elucidate sorptive properties of biochar changed with pyrolytic temperatures. The structural characteristics and isotherms shape of the biochar were more dependent on the pyrolytic temperature than on the biomass feedstocks, which included orange peel, pine needle, and sugar cane bagasse. For LTB, the thermally altered organic matter colocalized with the carbonized matter, and the visible fine pores of the fixed carbons were plugged by the remaining volatile carbon. For HTB, most of the volatile matter was gone and the fixed matter was composed of fully carbonized adsorptive sites. Monolayer adsorption of 1-naphthol to HTB was dominant but was suppressed by phenol. In comparison, LTB displayed exceptional sorption behavior where partition and adsorption were concurrently promoted by a cosolute and elevated temperature. In addition to monolayer surface coverage, pore-filling mechanisms may contribute to the increase of adsorption fraction. Moreover, the entropy gain was a dominant force driving the partition and adsorption processes in LTB. Thus, the colocalizing partition phase and adsorptive sites in LTB are proposed to be in interencased states rather than in physical separation

Insight into Multiple and Multilevel Structures of Biochars and Their Potential Environmental Applications: A Critical Review

Biochar is the carbon-rich product of the pyrolysis of biomass under oxygen-limited conditions, and it has received increasing attention due to its multiple functions in the fields of climate change mitigation, sustainable agriculture, environmental control, and novel materials. To design a “smart” biochar for environmentally sustainable applications, one must understand recent advances in biochar molecular structures and explore potential applications to generalize upon structure–application relationships. In this review, multiple and multilevel structures of biochars are interpreted based on their elemental compositions, phase components, surface properties, and molecular structures. Applications such as carbon fixators, fertilizers, sorbents, and carbon-based materials are highlighted based on the biochar multilevel structures as well as their structure-application relationships. Further studies are suggested for more detailed biochar structural analysis and separation and for the combination of macroscopic and microscopic information to develop a higher-level biochar structural design for selective applications

Full Biomass-Derived Solar Stills for Robust and Stable Evaporation To Collect Clean Water from Various Water-Bearing Media

Solar steam generation is considered to be a promising strategy for sustainable clean water supply. An easily made and robust solar still can practically meet any contingency in wilderness survival, compared to high-cost and delicate solar thermal materials, for example, plasmonic metals, carbon nanotubes, or graphene-based materials. Inspired by rice plants with high transpiration, we develop a universal solar steam-generation device from wasted rice straw for robust clean water production. The upper leaves of rice straw are carbonized and composited with bacterial cellulose to function as a superior light absorber and the lower culms are designed as excellent water pumps. The unique capillary structures and multilevel geometrical structures of the rice culms contribute to their outstanding water pumping capacity for surface evaporation, resulting in an evaporation rate of 1.2 kg m–2 h–1 with 75.8% conversion efficiency. The rice straw-derived solar still has a daily clean water yield of 6.4–7.9 kg m–2 on sunny days and 4.6–5.6 kg m–2 on cloudy days over 14 days of operation. More attention-grabbing aspect is that this evaporation device is applicable to various water-bearing media, for example, sand, soil, and seawater, to collect clean water with a stable evaporation performance, and the unique multilevel structures of the culms make great contribution to the unimpeded water channels. By turning “waste” to “wealth,” this project shines significant light on a facilely fabricated, robust, and efficient solar still, especially designed for urgent priority in wilderness survival