Cellulose nanofibrils(CNFs)are promising sustainable materials that can be applied to nanocomposites,as well as medical and life-sciences devices.However,methods for the preparation of these important materials are en...Cellulose nanofibrils(CNFs)are promising sustainable materials that can be applied to nanocomposites,as well as medical and life-sciences devices.However,methods for the preparation of these important materials are energy intensive because heating and mechanical disintegration are required to produce cellulose fibers below 100 nm in size.In this study,CNFs were prepared through the multi-site regioselective oxidation of cellulose with 2,2,6,6-tetramethylpiperidine-1-oxyl(TEMPO)and periodate at room temperature(20–25°C),without any mechanical-disintegration treatment.Transmission electron microscopy(TEM)revealed that the CNFs had the average widths of 14.1,55.4,and 81.9 nm for three different treatments.Fourier-transform infrared spectroscopy revealed that carboxyl groups were created on the surfaces of the microfibrils,while X-ray diffraction studies showed that the cellulose I structure was maintained after oxidation,and that the cellulose nanofibril crystallinity index exceeded 70%.These results demonstrate that CNFs can be prepared by multi-site regioselective oxidation at room temperature in the absence of mechanical disintegration.In addition,a model was developed to calculate the total content of carboxylate and aldehyde groups of CNFs prepared by the TEMPO mediate oxidation,the periodate oxidation,and the multi-site regioselective oxidation methods based on the particle width determined by TEM.The calculated values of the model were in good agreement with the total content(experimental value)of carboxylate and aldehyde groups of CNFs prepared by the TEMPO-mediated oxidation and the multi-site regioselective oxidation methods.However,the model was not valid for CNFs prepared by the periodate oxidation method.展开更多
Agricultural waste straw is the renewable resource with the highest annual yield in the world.In value-added applications of agricultural waste,dicarboxyl cellulose nanocrystals(DCCs)are prepared from rice,wheat,and c...Agricultural waste straw is the renewable resource with the highest annual yield in the world.In value-added applications of agricultural waste,dicarboxyl cellulose nanocrystals(DCCs)are prepared from rice,wheat,and corn straw by sequential periodate-chlorite oxidation.In this study,DCCs from rice,wheat,and corn straw were characterized by transmission electron microscopy(TEM),Fourier transform infrared spectrometer,X-ray diffractometer(XRD),and thermal gravimetric analysis(TGA).The carboxyl content of the DCCs was also investigated.XRD results show that the crystallinity index decreased after sequential periodate-chlorite oxidation;however,the cellulose I structure was maintained.TEM results show that rod-shaped DCCs with an average length and width of 287.0 nm and 9.9 nm,respectively,were successfully prepared by sequential periodate-chlorite oxidation.The carboxyl content of the DCCs was around 3.9 mmol/g,and not affected by the type of straw.Experiments to study the removal of copper ions in aqueous medium were performed with the prepared DCCs.The adsorption capacities of copper ions were 131,162,and 144 mg/g for DCCs prepared from rice,wheat,and corn straws,respectively.The results show that DCCs prepared from rice,wheat,and corn straws by sequential periodatechlorite oxidation have potential for the removal of copper ions from aqueous medium.展开更多
The accumulation of Cu^(2+)in water is a potential threat to human health and environment.Dicarboxylic nano-cellulose(DNC)with rich carboxyl groups was prepared through the NaIO_(4)–NaClO_(2) sequential oxidation met...The accumulation of Cu^(2+)in water is a potential threat to human health and environment.Dicarboxylic nano-cellulose(DNC)with rich carboxyl groups was prepared through the NaIO_(4)–NaClO_(2) sequential oxidation meth-od to efficiently remove copper ions,and the Cu 2+adsorption properties and cost were studied.The maximum adsorption capacity reached 184.2 mg/g at pH 6 and an adsorbent dose of 5 g/L.Theoretically,the maximum adsorption capacities of monocarboxylic nanocellulose(MNC),DNC,and tricarboxylic nanocellulose(TNC)with carboxyl groups as the main adsorption sites were calculated to be 228.7,261.3,and 148.1 mg/g,respectively.The Cu^(2+)adsorption costs of MNC,DNC,and TNC were calculated and compared with those of powdered activated carbon(PAC).The Cu^(2+)adsorption capacity of DNC is higher than that of PAC,and the adsorption cost is close to or lower than that of PAC,demonstrating that the DNC prepared by sequential oxidation of NaIO_(4)–NaClO_(2) has competitive adsorption capacity and cost in the treatment of wastewater containing Cu^(2+).展开更多
基金This research was funded by The Talents Project for Harbin Science and Technology Innovation,grant number 2016RAXXJ006China Postdoctoral Science Foundation,grant number 2017M611341.
文摘Cellulose nanofibrils(CNFs)are promising sustainable materials that can be applied to nanocomposites,as well as medical and life-sciences devices.However,methods for the preparation of these important materials are energy intensive because heating and mechanical disintegration are required to produce cellulose fibers below 100 nm in size.In this study,CNFs were prepared through the multi-site regioselective oxidation of cellulose with 2,2,6,6-tetramethylpiperidine-1-oxyl(TEMPO)and periodate at room temperature(20–25°C),without any mechanical-disintegration treatment.Transmission electron microscopy(TEM)revealed that the CNFs had the average widths of 14.1,55.4,and 81.9 nm for three different treatments.Fourier-transform infrared spectroscopy revealed that carboxyl groups were created on the surfaces of the microfibrils,while X-ray diffraction studies showed that the cellulose I structure was maintained after oxidation,and that the cellulose nanofibril crystallinity index exceeded 70%.These results demonstrate that CNFs can be prepared by multi-site regioselective oxidation at room temperature in the absence of mechanical disintegration.In addition,a model was developed to calculate the total content of carboxylate and aldehyde groups of CNFs prepared by the TEMPO mediate oxidation,the periodate oxidation,and the multi-site regioselective oxidation methods based on the particle width determined by TEM.The calculated values of the model were in good agreement with the total content(experimental value)of carboxylate and aldehyde groups of CNFs prepared by the TEMPO-mediated oxidation and the multi-site regioselective oxidation methods.However,the model was not valid for CNFs prepared by the periodate oxidation method.
文摘Agricultural waste straw is the renewable resource with the highest annual yield in the world.In value-added applications of agricultural waste,dicarboxyl cellulose nanocrystals(DCCs)are prepared from rice,wheat,and corn straw by sequential periodate-chlorite oxidation.In this study,DCCs from rice,wheat,and corn straw were characterized by transmission electron microscopy(TEM),Fourier transform infrared spectrometer,X-ray diffractometer(XRD),and thermal gravimetric analysis(TGA).The carboxyl content of the DCCs was also investigated.XRD results show that the crystallinity index decreased after sequential periodate-chlorite oxidation;however,the cellulose I structure was maintained.TEM results show that rod-shaped DCCs with an average length and width of 287.0 nm and 9.9 nm,respectively,were successfully prepared by sequential periodate-chlorite oxidation.The carboxyl content of the DCCs was around 3.9 mmol/g,and not affected by the type of straw.Experiments to study the removal of copper ions in aqueous medium were performed with the prepared DCCs.The adsorption capacities of copper ions were 131,162,and 144 mg/g for DCCs prepared from rice,wheat,and corn straws,respectively.The results show that DCCs prepared from rice,wheat,and corn straws by sequential periodatechlorite oxidation have potential for the removal of copper ions from aqueous medium.
文摘The accumulation of Cu^(2+)in water is a potential threat to human health and environment.Dicarboxylic nano-cellulose(DNC)with rich carboxyl groups was prepared through the NaIO_(4)–NaClO_(2) sequential oxidation meth-od to efficiently remove copper ions,and the Cu 2+adsorption properties and cost were studied.The maximum adsorption capacity reached 184.2 mg/g at pH 6 and an adsorbent dose of 5 g/L.Theoretically,the maximum adsorption capacities of monocarboxylic nanocellulose(MNC),DNC,and tricarboxylic nanocellulose(TNC)with carboxyl groups as the main adsorption sites were calculated to be 228.7,261.3,and 148.1 mg/g,respectively.The Cu^(2+)adsorption costs of MNC,DNC,and TNC were calculated and compared with those of powdered activated carbon(PAC).The Cu^(2+)adsorption capacity of DNC is higher than that of PAC,and the adsorption cost is close to or lower than that of PAC,demonstrating that the DNC prepared by sequential oxidation of NaIO_(4)–NaClO_(2) has competitive adsorption capacity and cost in the treatment of wastewater containing Cu^(2+).
