Wang Qin, Liu Shanshan, Wang Hong, Yang Yajiang
School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China.
Phys Chem Chem Phys. 2016 May 14;18(18):12610-5. doi: 10.1039/c6cp00872k. Epub 2016 Apr 19.
An aqueous mixture of sodium carbonate (Na2CO3) and sodium alginate (Na-ALG) was added dropwise into an aqueous solution of Ca(NO3)2, leading to the formation of calcium alginate (Ca-ALG) hydrogel beads. Meanwhile Na2CO3 as a pore-forming precursor was transformed in situ into CaCO3 nanoparticles (CaCO3 NPs). SEM images show that CaCO3 NPs aggregates with a size of ∼10 μm were uniformly distributed in the Ca-ALG hydrogel beads. After subsequent erosion using acetic acid, Ca-ALG hydrogel beads with a uniform microporous structure were obtained. The porosity and specific surface area of such in situ pore-formed hydrogel beads are 16 and 14 times higher than those of the beads prepared in the absence of Na2CO3. Additionally, their porous structure can be modulated by varying the amount of Na2CO3. The obtained porous Ca-ALG hydrogel beads were further immersed into an aqueous solution of AgNO3. Under UV irradiation, the Ag(+) ions adsorbed in the Ca-ALG were in situ reduced to Ag nanoparticles (Ag NPs). SEM and TEM images show that Ag NPs with a size of ∼10 nm were uniformly distributed in the matrix of the hydrogel beads. The loading amount of Ag in the beads can also be modulated by varying the amount of Na2CO3. Furthermore, the resultant Ca-ALG beads loaded with Ag NPs (Ag/Ca-ALG) were used as catalysts. Their catalytic activity was evaluated by using the reduction reaction of 4-nitrophenol as a model reaction. The rate constant of the reaction in the presence of dry porous Ag/Ca-ALG beads was found to be 36 times higher than that in the presence of beads prepared in the absence of Na2CO3. Such a high catalytic efficiency can be attributed to their porous structure and consequent high Ag-loading capacity.
将碳酸钠(Na₂CO₃)和海藻酸钠(Na-ALG)的水性混合物逐滴加入到硝酸钙(Ca(NO₃)₂)水溶液中,导致形成海藻酸钙(Ca-ALG)水凝胶珠。同时,作为成孔前体的Na₂CO₃原位转化为碳酸钙纳米颗粒(CaCO₃ NPs)。扫描电子显微镜(SEM)图像显示,尺寸约为10μm的CaCO₃ NPs聚集体均匀分布在Ca-ALG水凝胶珠中。在随后用乙酸侵蚀后,获得了具有均匀微孔结构的Ca-ALG水凝胶珠。这种原位成孔水凝胶珠的孔隙率和比表面积分别比在无Na₂CO₃情况下制备的珠子高16倍和14倍。此外,它们的多孔结构可以通过改变Na₂CO₃的量来调节。将所得的多孔Ca-ALG水凝胶珠进一步浸入硝酸银(AgNO₃)水溶液中。在紫外光照射下,吸附在Ca-ALG中的Ag⁺离子原位还原为银纳米颗粒(Ag NPs)。SEM和透射电子显微镜(TEM)图像显示,尺寸约为10nm的Ag NPs均匀分布在水凝胶珠的基质中。珠子中Ag的负载量也可以通过改变Na₂CO₃的量来调节。此外,所得负载Ag NPs的Ca-ALG珠(Ag/Ca-ALG)用作催化剂。通过使用4-硝基苯酚的还原反应作为模型反应来评估它们的催化活性。发现在干燥的多孔Ag/Ca-ALG珠存在下反应的速率常数比在无Na₂CO₃情况下制备的珠子存在下高36倍。如此高的催化效率可归因于它们的多孔结构和随之而来的高Ag负载能力。