Effect of oxygen-containing functional group contents on sorption of lead ions by acrylate-functionalized hydrochar.

The surface functional groups of hydrochar are crucial to its surface properties, and their contents are strongly positively correlated with the adsorption performance. In this study, acrylate-functionalized hydrochar (AHC) with varying contents of O-containing functional groups (OFGs) was synthesized via hydrothermal carbonization (HTC) of bamboo, acrylic acid and an initiator, and then deprotonated with NaOH. The AHCs were analyzed by various characterization techniques. During HTC, the higher amount of acrylic acid added led to higher carbon, oxygen and carboxyl contents, and to the larger specific surface area and pore volume of AHC. The adsorption kinetics, isotherms, thermodynamic, ionic strength and pH effects of Pb(II) on AHC were studied. Adsorption isotherms and kinetics obeyed Langmuir and pseudo-second-order models, respectively, indicating adsorption is monolayer chemical process. The adsorptive ability was well linearly related to the OFG contents of AHC. When acrylic acid was added to 25 mL during HTC, the adsorbing ability of AHC over Pb(II) reached 193.90 mg g-1. Hence, direct HTC of acrylic acid, biomass and an initiator can prepare hydrochar with controllable OFG contents, which is a prospective adsorbent for treating metal cations.

Effects of cation types in persulfate on physicochemical and adsorptive properties of biochar prepared from persulfate-pretreated bamboo.

The adsorption behaviors of biochar are largely impacted by biomassfeedstock. In this study, two biochars were prepared from torrefaction of ammonium persulfate- and potassium persulfate-pretreated bamboo and then activated by cold alkali, which are named as ASBC and KSBC, respectively. The two biochars were characterized by different instruments, and their adsorption properties over cationic methylene blue (MB) were compared. The type of persulfates little affected the specific surface areas, but significantly impacted O (29.54 % vs. 35.113 %) and N (12.13 % vs. 3.74 %) contents, functional groups, and zeta potentials of biochars. MB adsorption onto ASBC/KSBC is a single-layer chemical endothermic process and ASBC/KSBC exhibit high adsorption capacity over MB (475/881 mg·g-1) at 303 K. Obviously, the sorption capacity of MB onto KSBC much surpasses that of MB onto ASBC. These results indicate biomass pre-treatment is a cheap and convenient method to prepare biochars with unique physicochemical and adsorptive properties.

Manipulation of crystallization nucleation and thermal degradation of PLA films by multi-morphologies CNC-ZnO nanoparticles.

Currently, the quest for more renewable and biodegradable materials is a scientific priority to address the problems of petroleum-based plastics are difficult to degrade. In this work, cellulose nanocrystals (CNC) have been used as a template and four morphologies of CNC-ZnO nanocomposites were prepared via a hydrothermal method, and CNC-ZnO/polylactic acid (PLA) composite films were obtained by solution casting. We find that CNC-ZnO nanocomposites as heterogeneous nucleating agents improved the crystallinity and the film with flower-like CNC-ZnO was improved by 2.4 %. Ea required for thermal degradation of the PLA films decreased to 66-81 % of that of neat PLA, calculated by the Kissinger method, the Friedman method, and the Flynn-Wall-Ozawa (FWO) method. The R2 model was the solid degradation mechanism of the PLA films, analyzed through the Coats-Redfern method and the Criado method. The H-bond content of the composite films was significantly reduced after thermal aging at 150 °C. We found that three-dimensional CNC-ZnO (ZnO-3) made more prominent contributions to the crystallization, thermal degradation, and thermal aging of PLA films than other dimensional. The thermal properties can be regulated by the dimension, size, and apparent morphology of CNC-ZnO nanoparticles.

Enhanced removal of Cr(VI) by polyethyleneimine-modified bamboo hydrochar.

Hydrochar is an environmentally friendly and cheap adsorbent, but its adsorption amounts for anions is very limited. The functionalized hydrochar can overcome this shortcoming. Herein, polyethyleneimine-modified hydrochar (PEI-HC) was synthesized from hydrothermal carbonization (HTC) of methyl acrylate and bamboo after addition of initiator ammonium persulfate, and then modified by polyethyleneimine (PEI), which was used to treat Cr(VI). PEI-HC was tested by XANES, EXAFS, SEM-EDS, XPS, FTIR, N2 sorption isotherms, zeta potential, and elemental analyses. The characterizations showed that PEI was successfully grafted onto hydrochar, and the PEI-HC was rich in N and O functional groups, which presented high Cr(VI) sorption ability (528.41 mg·g-1 at pH 2). The bath experiments found the pseudo-second-order kinetic and Freundlich equations can well describe the adsorption kinetics and isotherm of the Cr(VI) adsorption onto PEI-HC, respectively. Electrostatic interaction, reduction, complexation, and H-bonding are the main removal mechanisms as supported by XANES, EXAFS, XPS, and FTIR. This study provides a strategy of combining HTC and free radical graft polymerization to convert agricultural and forestry wastes into functionalized hydrochar, showing highly efficient removal of Cr(VI).

Adsorption of lead ions and methylene blue on acrylate-modified hydrochars.

Hydrochars are promising sorbents for wastewater treatment. Herein, two acrylate-modified hydrochars (AMHC1 and AMHC2) were obtained by grafting acrylic acid on the surface of two hydrochars (MHC1 and MHC2 hydrothermally carbonized in water and acidic medium respectively) with free radical polymerization. Characterizations show that MHC2 is more prone to free radical polymerization than MHC1 does, and has higher carboxylate content after modification. The adsorption amounts of AMHC2 over methylene blue (MB) and Pb(II) are much higher than those of AMHC1. Pseudo-second-order kinetic and Langmuir isotherm equations well fit the Pb(II) and MB sorption data of AMHC2. The Pb(II) adsorptive mechanism is mainly inner-surface complexation accompanied by ion exchange and cation-π interaction. MB adsorption involves ion exchange, electrostatic interaction, H-bonding and π-π interaction. Hence, the one-step modification method of free radical polymerization under alkaline condition has great potential for preparing carboxylate-modified hydrochars to adsorb cationic pollutants.

Facile solvent-free radical polymerization to prepare itaconate-functionalized hydrochar for efficient sorption of methylene blue and Pb(II).

An itaconate-functionalized hydrochar (IFHC) was prepared from one-step solvent-free radical copolymerization of bamboo hydrochar, itaconic acid, ammonium persulphate and sodium hydroxide in solvent-free environment, and was employed to absorb methylene blue (MB) and Pb(II) from wastewater. Characterizations show IFHC has rich carboxylate and tends to adsorb cationic contaminants. The largest adsorbed quantities of MB and Pb(II) by IFHC are up to 1036 and 291.8 mg·g-1 at 298 K respectively as per the Langmuir isotherm. Sorption of MB and Pb(II) onto IFHC can be expressed well by Langmuir isotherm and pseudo-2nd-order kinetics equations. The high sorption performance depends on the rich carboxylate, which can adsorb MB/Pb(II) through an electrostatic interaction/inner-surface complexation mechanism. The sorptive capacity of regenerated IFHC decreased below 10% after 5 desorption-resorption cycles. Thus, the solvent-free free radical copolymerization is an environmentally-friendly strategy to synthesize novel efficient sorbents that can clean cationic contaminants from wastewater.

Multiple roles of ferric chloride in preparing efficient magnetic hydrochar for sorption of methylene blue from water solutions.

Highly efficient and cheap magnetic materials have application prospects in wastewater treatment. Herein, Fe3O4-loaded hydrochar (HC-Fe3O4) was obtained from hydrothermal carbonization (HTC) of bamboo with FeCl3 and then added with FeCl3 to form a magnetic sorbent via simple precipitation. The HC-Fe3O4 was characterized with various instruments. The characterizations show FeCl3 plays at least two roles as a catalyst and an oxidant in HTC. The specific surface area of hydrochar enlarged from 39.9731 to 60.9887 m2·g-1 after the addition of FeCl3 during HTC, which showed FeCl3 acted as a catalyst in HTC. XRD indicated Fe3O4 was formed by the structure of HC-Fe3O4, which indicated Fe(III) was reduced to Fe(II) during HTC. Sorption of methylene blue (MB) onto HC-Fe3O4 was better fitted by the Langmuir isotherm and pseudo-second-order kinetic models. Sorption is a spontaneous thermodynamic endothermic process and HC-Fe3O4 is easily separated by an applied magnetic field and reused.

A pyridinium functionalization chitosan for efficient elimination of methyl orange and Cr(VI).

A pyridinium functionalization chitosan (PCS) at high yield was facilely and solvothermally obtained from reactions of chitosan with N-2,4-dinitrophenyl-pyridinium chloride. The morphology and physical-chemical properties of PCS were tested with various techniques. Its sorption behaviors towards methyl orange (MO) and Cr(VI) were systematically investigated. Pseudo-second-order kinetic and Langmuir equations well fitted the sorption kinetics and isotherms, respectively. Thermodynamics analyses revealed the spontaneous and endothermic sorption of these two contaminants. PCS exhibited high sorption capacity of 1649.30 mg·g-1 MO and 200.46 mg·g-1 Cr(VI) at 308 K. The superior sorption performance of PCS over MO is ascribed to ion exchange, intermolecular hydrogen bond, and electrostatic and π-π interactions, while sorption of PCS over Cr(VI) is mainly driven by electrostatic forces, reduction and ion exchange. Moreover, the PCSexceeded 95 % of its original capacities during five cycles. This high sorption capacities and high reusability make PCS an excellent sorbent candidate towards anionic contaminants.

Motor cortical output for skilled forelimb movement is selectively distributed across projection neuron classes.

The interaction of descending neocortical outputs and subcortical premotor circuits is critical for shaping skilled movements. Two broad classes of motor cortical output projection neurons provide input to many subcortical motor areas: pyramidal tract (PT) neurons, which project throughout the neuraxis, and intratelencephalic (IT) neurons, which project within the cortex and subcortical striatum. It is unclear whether these classes are functionally in series or whether each class carries distinct components of descending motor control signals. Here, we combine large-scale neural recordings across all layers of motor cortex with cell type-specific perturbations to study cortically dependent mouse motor behaviors: kinematically variable manipulation of a joystick and a kinematically precise reach-to-grasp. We find that striatum-projecting IT neuron activity preferentially represents amplitude, whereas pons-projecting PT neurons preferentially represent the variable direction of forelimb movements. Thus, separable components of descending motor cortical commands are distributed across motor cortical projection cell classes.

Enhanced removal of Cr(VI) by cation functionalized bamboo hydrochar.

Chemical modification on hydrochars can significantly improve their ability of removing heavy metal ions from wastewater, but so far no research has focused on the chemical modification through free radical reaction. In this work, a cation functionalized hydrochar (CFHC) bearing - N+H2R was synthesized by grafting-polymerization of glycidyl methacrylate (GMA) onto bamboo hydrochar under initiation by benzoyl peroxide, followed by the amination with the introduced epoxy group and diethylenetriamine and a subsequent hydrochloric acid treatment. The resulted CFHC exhibited a superior removal capacity of 424.09 mg·g-1 for Cr(VI), and the highest sorption occurred at pH of 2. Combining a series of characterizations and tests, it was concluded that the sorption conformed to the pseudo-second-order and Freundlich equations, indicating a multilayer chemisorption process that mainly driven by electrostatic reaction, reduction, and surface complexation. This research proved that a free radical polymerization treatment could effectively transform hydrochars into super adsorbents for wastewater treatment.

Efficient adsorption of methylene blue on carboxylate-rich hydrochar prepared by one-step hydrothermal carbonization of bamboo and acrylic acid with ammonium persulphate.

Hydrochar (AAHC) with rich carboxylate groups was prepared by one-step hydrothermal carbonization (HTC) of bamboo and acrylic acid with the presence of ammonium persulphate, and then activated by a sodium hydroxide solution. AAHC was featured by elemental analysis, SEM, XPS, FTIR, Zeta potential analysis and N2 adsorption-desorption isotherms, and applied to test adsorptive ability of methylene blue (MB) by batch sorption experiments. Despite a small Brunauer-Emmett-Teller (BET) surface area of 5.03 m2·g-1, AAHC has excellent MB adsorbing capacity owing to the richness of carboxylate groups. Compared with hydrochar produced without adding ammonium persulphate, AAHC exhibits larger BET surface, pore volume and carboxylate groups, indicating a small amount of ammonium persulfate plays an important role in HTC in addition to the free radical initiator. This work provides a facile and cheap method combining HTC and polymerization for preparation of carboxylate-rich hydrochar.

Enhanced removal of Cr(VI) by nitrogen-doped hydrochar prepared from bamboo and ammonium chloride.

N-doped biochar can effectively eliminate toxic Cr(VI). Here, N-doped hydrochar (NHC) was successfully synthesized by one-pot hydrothermal carbonization (HTC) of NH4Cl and bamboo, and employed to adsorb Cr(VI). The specific surface area, pore volume, and carbon and nitrogen contents of NHC all increase compared with the undoped hydrochar (HC). NH4Cl acts as a cheap nitrogen source to enhance the nitrogen content of hydrochar and as an acid catalyst to accelerate hydrochar carbonization. Adsorption experiments show NHC has higher adsorption capacity than HC for Cr(VI). XPS and FTIR imply the dominant mechanisms of adsorbing Cr(VI) onto two hydrochars are electrostatic attraction, reduction and complexation, but the contributions of surface functional groups in two hydrochars for elimination of Cr(VI) differ. The doped nitrogen in NHC is pivotal in adsorbing and reducing Cr(VI). Hence, NHC prepared from bamboo and NH4Cl by one-step HTC is a cheap and efficient adsorbent to eliminate aqueous Cr(VI).

Disrupting cortico-cerebellar communication impairs dexterity.

To control reaching, the nervous system must generate large changes in muscle activation to drive the limb toward the target, and must also make smaller adjustments for precise and accurate behavior. Motor cortex controls the arm through projections to diverse targets across the central nervous system, but it has been challenging to identify the roles of cortical projections to specific targets. Here, we selectively disrupt cortico-cerebellar communication in the mouse by optogenetically stimulating the pontine nuclei in a cued reaching task. This perturbation did not typically block movement initiation, but degraded the precision, accuracy, duration, or success rate of the movement. Correspondingly, cerebellar and cortical activity during movement were largely preserved, but differences in hand velocity between control and stimulation conditions predicted from neural activity were correlated with observed velocity differences. These results suggest that while the total output of motor cortex drives reaching, the cortico-cerebellar loop makes small adjustments that contribute to the successful execution of this dexterous movement.

Preparation of hydrochar with high adsorption performance for methylene blue by co-hydrothermal carbonization of polyvinyl chloride and bamboo.

Polyvinyl chloride (PVC) was blended into bamboo powder during co-hydrothermal carbonization (Co-HTC) to understand the effects on the physicochemical properties and adsorbing ability of hydrochar. The properties of hydrochar were characterized by Zeta potential, elemental analyses, BET, FTIR, XPS, Boehm titration and SEM. The addition of PVC into bamboo in Co-HTC decreased the BET area, and pore volume and radius of hydrochar, but increased the contents of surface hydroxyl and carboxyl groups. The adsorption ability of hydrochar produced by addition of PVC at 473 K over methylene blue (MB) increased significantly. The main adsorption mechanism was electrostatic attraction by -N(CH3)2+ of MB and carboxylate of hydrochar, and hydrogen-bonding interaction through N atom of phenothiazine in MB and C-OH of hydrochar. Thus, Co-HTC offers a facile, green and economical alternative for conversion of waste into high-value adsorbents.

High effective adsorption of Pb(II) from solution by biochar derived from torrefaction of ammonium persulphate pretreated bamboo.

Biochar was prepared by torrefaction of ammonium persulphate pretreated bamboo (labeled as APBC) and applied into elimination of Pb(II) from water solutions. APBC was characterized by N2 adsorption-desorption isotherms, elemental and Zeta potential analyses, SEM-EDS, XPS, and FTIR. Abundant N- and O-containing groups appeared atop APBC. Batch sorption assays revealed that APBC had high affinity and strong sorption ability towards Pb(II). The high Pb(II) adsorbing ability was attributed to the high contents of N- and O-containing functional groups of APBC. The adsorption mechanism mainly occurred by inner-sphere surface complexation. Hence, torrefaction of ammonium persulphate pretreated bamboo is a promising strategy for producing efficient biochar that is applicable for industrial wastewater treatment.

Selective removal of anionic and cationic dyes by magnetic Fe3O4-loaded amine-modified hydrochar.

Fe3O4-loaded protonated amine-modified hydrochar (Fe3O4-PAMH) was successfully prepared and characterized by scan electron microscopy equipped with energy-dispersion X-ray spectroscopy, zeta potential analysis, vibration sample magnetometry, Fourier transform infrared and X-ray photoelectron spectroscopies, Brunauer-Emmett-Teller measurement, and X-ray diffraction. Adsorption properties of Fe3O4-PAMH to negatively-charged methyl orange (MO) or positively-charged methylene blue (MB) in one- or two-component systems were evaluated. The Fe3O4-PAMH selectively adsorbed MO and MB at pH 5 and 11, respectively. The maximum MO and MB uptake capacities of Fe3O4-AMHC were 202.02 mg/g (pH 5.0) and 148.84 mg/g (pH 11) respectively. The Fe3O4-PAMH can be reused with simple pH management in adsorption-desorption cycles. The MB and MO adsorption abilities on Fe3O4-PAMH were maintained above 99% and 75% for five consecutive recycles, respectively. Thus, Fe3O4-PAMH shows powerful potential in efficiently and selectively adsorbing anionic or cationic dyes from mixed wastewater.

Removal of aqueous-phase lead ions by dithiocarbamate-modified hydrochar.

Hydrochar produced from agricultural and forestry wastes and its application into the environment are very attractive. Herein, a high-efficiency dithiocarbamate-modified hydrochar (DTHC) was prepared successfully and then applied to eliminate Pb(II) from aqueous solutions. DTHC was characterized by various techniques. It was found that dithiocarbamate and amine groups were successfully grafted onto the surface of hydrochar. The surface area of DTHC was 7.94 m2·g-1, which was four folds less than pristine hydrochar (31.60 m2·g-1), but its adsorption capacity obviously increased. Adsorption experiments showed that the Pb(II) adsorption process onto DTHC well accorded with pseudo-2nd-order kinetics and Langmuir isotherms. The highest Pb(II) uptake by DTHC at 293 K determined from the Langmuir model was 151.51 mg·g-1. Fourier transform infrared spectra and X-ray photoelectron spectroscopy verified that dithiocarbamate, carboxylate, amine and sulfonate groups all facilitated the Pb(II) adsorption. The adsorption mechanism was ascribed to the inner-sphere surface complexation of Pb(II) by these groups and to the ion exchange between Pb(II) and Na(I). Thus, DTHC is an effective adsorbent for Pb(II) removal from water.

Cortical pattern generation during dexterous movement is input-driven.

The motor cortex controls skilled arm movement by sending temporal patterns of activity to lower motor centres1. Local cortical dynamics are thought to shape these patterns throughout movement execution2-4. External inputs have been implicated in setting the initial state of the motor cortex5,6, but they may also have a pattern-generating role. Here we dissect the contribution of local dynamics and inputs to cortical pattern generation during a prehension task in mice. Perturbing cortex to an aberrant state prevented movement initiation, but after the perturbation was released, cortex either bypassed the normal initial state and immediately generated the pattern that controls reaching or failed to generate this pattern. The difference in these two outcomes was probably a result of external inputs. We directly investigated the role of inputs by inactivating the thalamus; this perturbed cortical activity and disrupted limb kinematics at any stage of the movement. Activation of thalamocortical axon terminals at different frequencies disrupted cortical activity and arm movement in a graded manner. Simultaneous recordings revealed that both thalamic activity and the current state of cortex predicted changes in cortical activity. Thus, the pattern generator for dexterous arm movement is distributed across multiple, strongly interacting brain regions.

Facile Synthesis of Calcite-Impregnated Hydrochar with High Sorption Capacity for Cu(II) from Aqueous Solution.

Calcite-impregnated hydrochar (Ca-HC) was successfully synthesized by a one-step hydrothermal method and used as an adsorbent for Cu(II) remediation. Characterization techniques showed that Ca-HC contained calcite and oxygen-containing functional groups. A series of Cu(II) sorption experiments onto Ca-HC showed that the initial Cu(II) concentration, contact time, sorption temperature, and initial pH of the solution influenced the sorption of Cu(II). The actual achievable sorption capacity of Ca-HC for Cu(II) was 130.57 mg g-1 at 303 K, and the sorption process obeyed the Langmuir model and pseudo-second-order kinetic equation. The precipitation and surface complexation rather than ion exchange were mainly ascribed to the removal of Cu(II) onto Ca-HC. The calcite provided the active site to produce posnjakite precipitation during the sorption process and enhance the sorption capacity of the hydrochar. Therefore, these results demonstrated that Ca-HC is an effective sorbent that can remove Cu(II) from water.

The polyaminocarboxylated modified hydrochar for efficient capturing methylene blue and Cu(II) from water.

The polyaminocarboxylated modified hydrochar (ACHC) was synthesized to introduce abundant amino, hydroxyl and carboxylate multifunctional groups onto the surface of hydrochar by etherification, amination and carboxylated reaction. The ACHC was systematically characterized and used to evaluate adsorption properties of Cu(II) and methylene blue (MB) by batch sorption tests. The adsorption process toward Cu(II) and MB by ACHC obeyed the pseudo-second-order kinetic model and Langmuir model. Characteristic analysis indicated the surface chelation was mainly contribute to Cu(II) adsorption by large amounts of amino and carboxylate groups while π-π interaction, hydrogen bonding and electrostatic attraction dominated MB adsorption. The maximum adsorption capacities of ACHC were 140.65 and 1238.66 mg·g-1 for Cu(II) and MB at 303 K, respectively. Approximately 97% of the adsorptive uptakes for two pollutants were removed within merely 5 min for kinetic experiment. Competitive adsorption of Cu(II) and MB, and treatment of electroplating wastewater by ACHC were also investigated.