Controllable Synthesis of Cobalt-Containing Nanosheet Array-Like Ternary CuCoAl-LDH/rGO Hybrids To Boost the Catalytic Efficiency for 4-Nitrophenol Reduction

A series of Co-doped ternary Cu_xCo_3-xAl-layered double hydroxide (LDH)/rGO nanosheet array hybrids (x = 0.5, 1.0, 1.5, and 2.0) were successfully prepared using the preconditioned pH value aqueous-phase coprecipitation strategy. The Cu_xCo_3-xAl-LDH/rGO hybrids are featured as hexagonal CuCoAl-LDH nanosheets in situ anchoring onto both sides of the rGO surface in an ab-plane vertically interlaced growth pattern. The Cu_xCo_3-xAl-LDH/rGO hybrids show excellent activity for the complete conversion of 4-nitrophenol to 4-aminophenol, especially Cu_1.5Co_1.5Al-LDH/rGO with the highest k_app value of 49.2 × 10^-3 s^-1 and TOF of 232.8 h^-1, clearly higher than most copper-containing samples in the literature and even some precious ones. Thermodynamic analysis was carried out, and the values of Ea, ΔH^#, ΔS^#, and ΔG^# were estimated. The best activity of Cu_1.5Co_1.5Al-LDH/rGO can be mainly ascribed to the in situ-formed ultrafine Cu₂O NPs (∼4.3 nm) along with a small amount of Cu⁰ species, the electron transfer effect induced by atomically dispersed Co²⁺ species leading to the formation of electron-rich Cu species along with the Co²⁺/Co³⁺ redox couple, the strong Cu₂O-CuCoAl-LDH-rGO synergy upon the nanosheet array morphology with a high surface area and pore volume, and enhanced adsorption of reactants upon π-π stacking via an rGO layer. Meanwhile, the Cu_1.5Co_1.5Al-LDH/rGO exhibits an excellent universality and good cycling stability for 10 continuous runs. The Cu_1.5Co_1.5Al-LDH/rGO also shows superior efficiency in the catalytic reduction of 4-NP solution with a high concentration (20 mM) and displays excellent reduction performance in the fixed-bed test, implying the potential applications of the current Co-doped hierarchical ternary Cu-based LDH/rGO hybrids in the continuous treatment of practical wastewater.