Nature's blueprint provides the fundamental principles for expanding the use of abundant metals in catalysis; however, mimicking both the structure and function of copper enzymes simultaneously in one artificial system for selective C−H bond oxidation faces marked challenges. Herein, we report a new approach to the assembly of artificial monooxygenases utilizing a binuclear Cu 2 S 2 Cl 2 cluster to duplicate the identical structure and catalysis of the Cu A enzyme. The designed monooxygenase Cu-Cl-bpyc facilitates well-defined redox potential that initially activated O 2 via photoinduced electron transfer, and generated an active chlorine radical via a ligand-to-metal charge transfer (LMCT) process from the consecutive excitation of the in situ formed copper(II) center. The chlorine radical abstracts a hydrogen atom selectively from C(sp 3 )−H bonds to generate the radical intermediate; meanwhile, the O 2•− species interacted with the mimic to form mixed-valence species, giving the desired oxidization products with inherent product selectivity of copper monooxygenases and recovering the catalyst directly. This enzymatic protocol exhibits excellent recyclability, good functional group tolerance, and broad substrate scope, including some biological and pharmacologically relevant targets. Mechanistic studies indicate that the C−H bond cleavage was the rate-determining step and the cuprous interactions were essential to stabilize the active oxygen species. The well-defined structural characters and the fine-modified catalytic properties open a new avenue to develop robust artificial enzymes with uniform and precise active sites and high catalytic performances.

The chemoselective hydrogenation of cinnamaldehyde (CAL) to the corresponding hydrocinamaldehyde (HCAL) is a type of important reactions in fine chemistry, which is critically dependent on the rational design the chemical structure of active metal. In this work, calcium promoted palladium on CNT hybrid (Ca-Pd@CNT) with monolithic structure was synthesized through one-pot alginate gel process. The catalytic performance results showed that moderate Ca promotion catalyst (Ca-Pd@CNTHCl−2h) present a superior CAL hydrogenation activity with CAL conversion of 99.9% and HCAL selectivity of 86.4% even at the lager Pd nanoparticle size (c.a. 5 nm). The characterization results show that the electron transfer between the additive Ca promoter and Pd nanoparticles (NPs) could modify the electron structure of Pd species and induce the formation of the partial positively charged Pdδ+ species on the Pd NPs surface in the Ca-Pd@CNTHCl−2h catalyst resulting to the satisfactory catalytic performance. Furthermore, the one-pot gel synthesis methodology for microscopic carbon supported catalyst could also endows its great potential industry application in heterogeneous catalysis with easily handling during the transportation and reaction, and attributed to reducing the overall pressure drop across in the fix-bed reactor.