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

Biochar is a carbon allotrope obtained by pyrolysis of biomass, usually agro-waste. Owing to the demand for sustainable development, biochar is continuously raising much hope in the scientific community. However, in order to impart it with new properties, its modification is required, either in situ during pyrolysis, or after the carbonization process. Herein, we propose a new direct approach to obtain bimetallic copper/nickel nanoparticle-loaded on olive stone biochar. The bimetallic-coated biochar and the reference materials bare biochar, copper-loaded and nickel-loaded biochar were prepared at 400 °C under a stream of dinitrogen from olive pit powder particles impregnated first with citric acid (CA), and then with copper and nickel nitrates. We have employed citric acid in the process in order to check 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-sized 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 nano-raspberries (1748 nm in size) which are agglomerates of individual 10-20 nm-sized 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 attracted efficiently with a magnet, but not B-CA@CuNi10/1 due to a 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 with exhibit as fast discoloration catalysis performance. This paper stresses the important role of citric acid in shaping the bimetallic nanoparticles loaded in situ on biochar during the slow pyrolysis process and to enable faster catalysed discoloration of organic dye solution.