Nanosheet array-like Cu@Cu2O-CuNiAl(O)/rGO composites for highly efficient reduction of nitrophenol: Electronic and structure promotion effect of nickel

Series of hierarchical nanosheet array-like composites xCu@Cu2O-CuNiAl(O)/rGO (x = 1.0, 1.5, 2.0) were constructed via proper calcination of pre-prepared hybrids Cu3Ni3-xAl-layered double hydroxide/rGO in N-2 flow, upon the LDH layer atomic-level lattice confined in situ self-reduction for Cu2+ ions by rGO substrate along with the dispersion effect of Ni-OH groups. Systematic characterizations reveal that core@shell-type Cu@Cu2O nanoparticles (NPs) are definitely trapped in the border space among the vertically adjacent CuNiAl(O) nanosheets and rGO substrates. All the xCu@Cu2O-CuNiAl(O)/rGO composites exhibit excellent catalytic activities for the reduction of 4-nitrophenol (4-NP), particularly 1.5Cu@Cu2O-CuNiAl(O)/rGO possesses the highest activity (k(app): 7.6 x 10(-2) s(-1), TOF: 265.0 h(-1)), and superb reusability with insignificant loss in activity for continuous 25 cycles, much better than those of recently reported Cu-based catalysts and even comparable to some noble metal catalysts. The best performance of 1.5Cu@Cu2O-CuNiAl(O)/rGO can be mainly attributed to the most uniformly dispersed electrophilic core@shell Cu@Cu2O NPs modified by NiO species structurally and electronically, the strongest Cu-Cu2O-CuNiAl(O)-rGO synergistic effect upon the unique nanosheet array-like morphology providing more ion-accessible active sites, and much improved adsorption for 4-NP via rGO layer due to pi-pi stacking. The universality and fixed bed tests further demonstrate potential practical applications of the present hierarchical non-noble composites for water remediation. The present facile synthesis strategy of the nanosheet array-like Cu@Cu2O-CuNiAl(O)/rGO composites with multi-phases synergy may be greatly beneficial to the design and construction of many other highly efficient multi-transition metal-based catalysts with excellent structural robustness for a broad range of applications in related catalysis processes.

Automated summary

A series of hierarchical nanosheet array-like composites were constructed with excellent catalytic activities for the reduction of 4-nitrophenol, especially the 1.5Cu@Cu2O-CuNiAl（O）/rGO composite. The best performance of the 1.5Cu@Cu2O-CuNiAl（O）/rGO can be mainly attributed to the most uniformly dispersed core@shell Cu@Cu2O NPs, strong synergistic effect among different components, and improved adsorption for 4-NP via rGO layer. This synthesis strategy may be beneficial for the design of other efficient multi-transition metal-based catalysts.