Synthesis and characterization of chitosan-copper nanocomposites and their catalytic properties for 4-nitrophenol reduction.

Biopolymer-based copper nanoparticles (CuNPs) have become an area of significant interest due to their wide-ranging applications in a variety of fields. However, there remains a challenge in tailoring their morphologies and improving their properties. In this study, CuNPs were synthesized via wet chemical reduction using sodium hypophosphite monohydrate (NaH2PO2·H2O), l-ascorbic acid and chitosan. The effect of different synthesis conditions, including reaction pH, temperature, time, concentration of NaH2PO2·H2O, l-ascorbic acid and chitosan, as well as the deacetylation degree (DD) of chitosan, on the synthesis of CuNPs was investigated. The synthesized CuNPs were characterized by various analytical techniques. The catalytic properties of synthesized CuNPs were investigated for the reduction of 4-nitrophenol (4-NP) in the presence of sodium borohydride. The synthesis-morphology-catalytic activity relationship of CuNPs was discussed. The results suggested that the morphology of CuNPs could be adjusted by controlling the synthesis conditions. Chitosan DD significantly impacts the morphology of the synthesized CuNPs. As the chitosan DD decreased from 91.8 % to 52.3 %, the average particle size of synthesized CuNPs decreased from 43.9 ± 10.6 to 17.7 ± 5.9 nm and the shape changed from anisotropy to near-sphere. CuNPs synthesized using low DD (53.2 %) chitosan (CuNPs-N3) demonstrated the highest 4-NP conversion rate of 99.1 % and reaction rate constant of 0.3540 min-1. CuNPs-N3 was thermodynamically and kinetically more feasible than CuNPs synthesized with high DD chitosan. These findings provide important insights for further designing and developing hierarchical nanostructured CuNPs catalysts for broader applications.

Green synthesis of reduced graphene oxide/chitosan/gold nanoparticles composites and their catalytic activity for reduction of 4-nitrophenol.

Gold nanoparticles (AuNPs) have attracted extensive attention in the past few years due to their unique properties and great potential application in catalysis. However, the application of AuNPs remains a significant challenge due to the lack of high efficiency and stability caused by aggregation. Immobilization of AuNPs on appropriate support shows promising results in avoiding aggregation and improving catalytic activity. In this work, reduced graphene oxide/chitosan/gold nanoparticles (rGO/CHS/AuNPs) composites were prepared using chitosan with different molecular weights (MW) as a reducing agent and stabilizer, and characterized by FT-IR, XRD, XPS, SEM, FESEM, EDS, TEM, HRTEM, and TGA. The preparation conditions of rGO/CHS/AuNPs composites, including chitosan MW, CHS/GO mass ratio, reaction temperature and time, and HAuCl4 concentration were investigated in detail. The results indicated that reduction activity of chitosan for GO increased with the decrease of chitosan MW. The C/O ratio of rGO reduced by low molecular weight chitosan (LMWC) with viscosity-average molecular weight (Mv) of 21 kDa was 6.34. Small spherical AuNPs were uniformly immobilized on the rGO surface. The particle size of AuNPs increased from 9.29 to 13.03 nm as chitosan MW decreased from 465 to 21 kDa. The rGO/CHS/AuNPs showed good catalytic activity for the reduction of 4-NP in the presence of NaBH4. The catalytic activity of rGO/CHS/AuNPs was closely related to chitosan MW. rGO/CHS/AuNPs synthesized by LMWC with Mv of 21 kDa showed the highest kinetic rate constant of 0.2067 min-1. The results of this experimental study could be useful in the development of effective catalysts for the reduction of aromatic nitro compounds.

Selenium distribution in cultivated Argosols and Gleyosols of dry and paddy lands: A case study in Sanjiang Plain, Northeast China.

Distribution pattern of selenium (Se) fractions in soil could influence Se content in crops and thereby intake of Se in human body. In order to investigate the effects of soil types and farming conditions on Se distribution in small-scaled cultivated land developed under the same conditions of climate, topography and parent materials, two types of soils (i.e., Argosols and Gleyosols) from paddy and dry lands in the Sanjiang Plain of Northeast China were selected. Total Se (T-Se) content in Argosols was influenced by organic carbon (Org C) content and pH of bulk topsoil. In Gleyosols, it was mainly affected by Org C content in dry land and pH in paddy land, respectively. In rice root associated topsoil, organic matter associated Se (OM-Se) accounted for 70% of T-Se. Compared with pH (median 6.10) and OM weakly bound Se (OW-Se) (0.14 ± 0.04 mg kg-1) of Argosols, the higher pH (median 6.77) resulted in less OW-Se (0.10 ± 0.04 mg kg-1) of Gleyosols. Vertical distribution of Se in borehole cores within the depth of 0-900 cm was mainly affected by the soil type. Se accumulated mainly within 0-150 cm depth (horizon A, E and B) in Argosols and above 40 cm depth (horizon H), existing prominently as OM strongly bound Se (OS-Se), in Gleyosols. Within the depth of 0-150 cm, various Se fractions for both soils were probably controlled by reductive fixation and complexation of Org C; In the alkaline paddy land, DOM-complexed Se was the main composition of A-Se. The findings of this study could help in understanding the mechanisms of Se distribution and enrichment in soils developed under different formation processes and farming conditions.

Experimental and modeling study of pure terephthalic acid (PTA) wastewater transport in the vadose zone.

PTA wastewater discharged from a factory was selected as the research object in this project and CODcr was selected as the characteristic pollution factor. Static adsorption and soil column leaching experiments of silty clay and clayey soil were carried out to study the adsorption, bio-degradation and dispersion coefficient of CODcr in PTA wastewater. Hydrus-1D was used to build the convection-diffusion model to demonstrate the migration of PTA wastewater in the vadose zone. The results indicate that silty clay and clayey soil in the vadose zone can adsorb, degrade and impede the contaminants in PTA wastewater; however, the coefficient of adsorption and degradation were very low, they were down to 0.0002 L g(-1), 0.0003 L g(-1) and 0.0097 d(-1), 0.0077 d(-1) for silty clay and clayey soil, respectively. Under the virtual condition that, wastewater in the sewage pool is 5 m deep, CODcr concentration is 4000 mg L(-1), vadose zone is 21 m, PTA wastewater will reach the phreatic surface after 20.87 years. When wastewater in the sewage pool is 7 m with other conditions unchanged, after 17.18 years PTA wastewater will reach groundwater. The results show that there is a higher pollution risk for groundwater if we do not take any anti-seepage measures.