Citric-Acid-Assisted Preparation of Biochar Loaded with Copper/Nickel Bimetallic Nanoparticles for Dye Degradation

Abstract

Immobilization of nanocatalysts on biochar is receiving unprecedented interest among material and catalysis scientists due to its simplicity, versatility, and high efficiency. Herein, we propose a new direct approach to obtain bimetallic copper/nickel nanoparticles loaded on olive stone biochar. The bimetallic-coated biochar and the reference materials, namely bare biochar, copper rich-loaded biochar, and nickel-loaded biochar, were prepared by pyrolysis from olive pit powder particles impregnated first with citric acid (CA) and then with copper and nickel nitrates at 400 °C under nitrogen flow. We employed citric acid in the process in order to examine its effect on the structural and textural properties of biochar supporting the metallic nanoparticles. Surprisingly, citric acid induced the formation of agglomerated or even raspberry-shaped bimetallic copper/nickel nanoparticles. Large 450–500 nm agglomerates of ~80 nm bimetallic CuNi NPs were noted for B-CA@CuNi. Interestingly, for biochar material prepared with initial Cu/Ni = 10 molar ratio (B-CA@CuNi10/1), the bimetallic NPs formed unusual nanoraspberries (174 ± 8 nm in size), which were agglomerates of individual 10–20 nm CuNi10/1 nanoparticles. The B-CA@CuNi and reference materials were characterized by Raman spectroscopy, scanning electron microscopy (SEM)/energy-dispersive X-ray spectroscopy (EDX), X-ray diffraction (XRD), and magnetometry. The B-CA@CuNi and B-CA@Ni materials could be efficiently attracted with a magnet but not B-CA@CuNi10/1 due to the low nickel loading. B-CA@CuNi was tested as a catalyst for the degradation of methyl orange (MO). Discoloration was noted within 10 min, much faster than a similar material prepared in the absence of CA. B-CA@CuNi could be recycled at least 3 times while still exhibiting the same fast catalytic discoloration performance. This paper stresses the important role of citric acid in shaping bimetallic nanoparticles loaded in situ on biochar during the slow pyrolysis process and in enabling faster catalytic discoloration of organic dye solution.