MnO_2基复合吸附剂制备及去除水中重金属性能
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摘要
采用共水热法和分步水热法分别制备了δ-MnO_2/MCM-41和δ-MnO_2/ZSM-5-n复合吸附材料,利用X射线衍射仪、透射电镜、N_2吸附/脱附仪等对复合吸附剂进行了表征,并考察了其去除水中Cu~(2+)和Ni~(2+)的性能。结果表明,δ-MnO_2具有海胆状形貌,单个颗粒直径大约在200 nm;其与分子筛复合后仍能保持原来的晶型和介孔结构。对δ-MnO_2/MCM-41复合吸附剂,当MCM-41添加质量分数为30%时,其对溶液中重金属Ni~(2+)吸附能力最大,约为44.61mg/g;对δ-MnO_2/ZSM-5-n复合吸附剂,其对重金属离子的吸附量随ZSM-5-n硅铝比的增大而降低;且复合吸附剂对溶液中的重金属离子以单层物理吸附为主。
The δ-MnO_2/MCM-41 and δ-MnO_2/ZSM-5-n composite adsorbents were prepared by co-hydrothermal method and stepwise hydrothermal method,respectively. The performance of obtained adsorbents for Cu~(2+) and Ni~(2+) removal from water were characterized using X-ray diffractometer, transmission electron microscope, and N_2 adsorption-desorption instrument. The results showed that, δ-MnO_2 had a sea urchin-like morphology with a single particle diameter of about 200 nm. After being compounded with the molecular sieve, the δ-MnO_2 could still maintain its original crystal structure and microporous structure. For δ-MnO_2/MCM-41 composite adsorbent, when the dosage of mass fraction of MCM-41 was 30%, its adsorption capacity for Ni~(2+) was the largest, about 46.61 mg/g; For δ-MnO_2/ZSM-5-n, its adsorption capacity of heavy metal ions decreased with increase of silica-alumina ratio of ZSM-5-n,and the heavy metal species were absorbed onto the composite adsorbents surface by forming a continuous monolayer of adsorbate molecules.
The δ-MnO_2/MCM-41 and δ-MnO_2/ZSM-5-n composite adsorbents were prepared by co-hydrothermal method and stepwise hydrothermal method,respectively. The performance of obtained adsorbents for Cu~(2+) and Ni~(2+) removal from water were characterized using X-ray diffractometer, transmission electron microscope, and N_2 adsorption-desorption instrument. The results showed that, δ-MnO_2 had a sea urchin-like morphology with a single particle diameter of about 200 nm. After being compounded with the molecular sieve, the δ-MnO_2 could still maintain its original crystal structure and microporous structure. For δ-MnO_2/MCM-41 composite adsorbent, when the dosage of mass fraction of MCM-41 was 30%, its adsorption capacity for Ni~(2+) was the largest, about 46.61 mg/g; For δ-MnO_2/ZSM-5-n, its adsorption capacity of heavy metal ions decreased with increase of silica-alumina ratio of ZSM-5-n,and the heavy metal species were absorbed onto the composite adsorbents surface by forming a continuous monolayer of adsorbate molecules.
引文
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[3]朱秋锋,王丽婷,安泽欢,等.不同形态氧化锰的水热制备及吸附重金属离子性能[J].化工新型材料,2016,6(44):184-186.
[4]常学秀,文传浩,王焕校.重金属污染与人体健康[J].云南环境科学,2000,19(1):59-61.
[5]WARNER C L,CHOUYYOK W,MACKIC K E,et al.Manganese doping of magnetic iron oxide nanoparticles:tailoring surface reactivity for a regenerable heavy metal sorbent[J].Langmuir,2012,28(8):3931-3937.
[6]张健,万东锦,刘永德,等.碱改性ZSM-5沸石分子筛吸附去除水中Pb的研究[J].环境工程技术学报,2015,5(4):277-283.
[7]ZHU Q F,WANG L T,AN Z H,et al.Hydrothermal synthesis of silico-manganese nanohybrid for Cu(II)adsorption from aqueous solution[J].Applied Surface Science,2016,371:102-111.
[8]ZHU Q F,ZHANG Q C,WEN L X.Anti-sintering silica-coating CuZnAlZr catalyst for methanol synthesis from CO hydrogenation[J].Fuel Processing Technology,2016,156:280-289.
[9]朱秋锋,郭贺靖,苏琳雯.硅锰复合物的水热合成及其对水中Cu2+的吸附[J].环境工程学报,2016,8(10):4221-4227.
[10]包一翔,谢小妮,周佳璐,等.氨基化MCM-41介孔分子筛改性超滤膜去除水中Cr(VI)的研究[J].华南师范大学学报(自然科学版),2015,47(6):58-62.
[11]LIU J T,GE X,YE X X,et al.3D graphene/delta-MnO2aerogels for highly efficient and reversible removal of heavy metal ions[J].Journal of Materials Chemistry A,2016,4(5):1970-1979.
[12]陈喻娟.二氧化锰的水热合成、形态表征及其电化学性能研究[D].广州:华南理工大学,2010.
[13]ZHAO,Y N.Review of the natural,modified,and synthetic zeolites for heavy metals removal from wastewater[J].Environmental Engineering Science,2016,33:443-454.
[14]FENG Y,WANG Y Q,WANG Y Y,et al.Simple fabrication of easy handling millimeter-sized porous attapulgite/polymer beads for heavy metal removal[J].Journal of Colloid and Interface Science,2017,502:52-58.
[15]ZHAO M H,XU Y,ZHANG C S,et al.New trends in removing heavy metals from wastewater[J].Applied Microbiology and Biotechnology,2016,100:6509-6518.
[16]ZOU W H,HAN R P,CHEN Z Z,et al.Kinetic study of adsorption of Cu(II)and Pb(II)from aqueous solutions using manganese oxide coated zeolite in batch mode[J].Colloids&Surfaces A Physicochemical&Engineering Aspects,2006,279(1/3):238-246.
[17]皇晓晨.高硅ZSM-5沸石分子筛负载纳米零价铁去除水溶液中重金属机理的研究[D].郑州:河南师范大学,2016.