3-D porous cellulose nanofibril aerogels with a controllable copper nanoparticle loading as a highly efficient non-noble-metal catalyst for 4-nitrophenol reduction.

Nitrophenols(NPs) are highly toxic compounds that occur in various industrial effluents. Herein, we investigated Cu nanoparticle-loaded cellulose nanofibril (CNF/PEI-Cu) aerogels as a catalyst for degrading 4-nitrophenol (4NP) in the wastewater. Non-noble metal based low-cost catalyst material and easily scalable preparation method make CNF/PEI-Cu aerogel as an appropriate catalyst for practical application in 4NP wastewater treatment. Our strategy to improve the loading amount of homogeneously distributed Cu nanoparticles was to functionalize a CNF aerogel using polyethylene imine (PEI), which can bind Cu2+ ions. Porous CNF aerogels with homogenously distributed 20-40 nm Cu nanoparticles were obtained by adsorbing Cu2+ ions and chemically reducing them to Cu metal. The FTIR, XRD, SEM, XPS and ICP-OES analysis were used to confirm the in-situ formation of Cu nanoparticles. In the presence of the CNF/PEI-Cu aerogels, 4NP was effectively reduced to 4-aminophenol (4AP) without loss of the Cu nanoparticles. The activation energy (Ea) and reaction rate constant (kapp) of the catalytic 4NP reduction reaction by the CNF/PEI2-Cu aerogels were calculated to be Ea = 39.56 kJ mol-1 and kapp = 0.770 min-1, respectively. The Ea is similar or even smaller than the Ea values of the corresponding reactions involving noble-metal catalysts, demonstrating that the CNF/PEI-Cu aerogels developed in the present study have strong potential as practical and economical catalysts.