Atomic Pd dispersion in triangular Cu nanosheets with dominant (111) plane as a tandem catalyst for highly efficient and selective electrodehalogenation

Chen，Huihuang1; Li，Hongbo1; Chen，Shaoqing2; Sheng，Li3; Zhang，Zhirong3; Wu，Wenlong3; Fan，Maohong4; Wang，Lianzhou5; Yang，Bo1

2023-07-05

10.1016/j.apcatb.2023.122480

APPLIED CATALYSIS B-ENVIRONMENTAL   影响因子和分区

0926-3373

1873-3883

Single-atom alloys (SAA) in which active metal atoms are atomically dispersed in an inert host possess unique geometric and electronic structures, and generally own higher catalytic performance than their monometallic counterparts. Whereas it is still challenging to facilely synthesize well-defined single atoms embedded in single crystals dominated with a specific active plane. Herein, we synthesized Pd single atoms anchored in triangular Cu nanosheets (PdCu SAA) with dominant active (111) plane via wet chemical synthesis and galvanic replacement as a high-performance catalyst for the electrocatalytic hydrodehalogenation (ECHD) of the refractory tribromophenol. Based on intensive theoretical calculations and experimental work, a hydrogen spillover mechanism was firstly proposed and verified for the highly efficient and selective ECHD. Hydrogen spillover occurs from the hydrogen-rich Pd to the hydrogen-deficient Cu host with a marginal kinetic energy barrier due to the short reaction distance and the negligible interfacial resistance. Meanwhile, the strong metal-support interaction between Pd and peripheral Cu optimizes the adsorption of hydrogenated products to allow for the further catalytic reaction. Consequently, by decoupling the ECHD process into hydrogen adsorption, hydrogen spillover and hydrodebromination, PdCu SAA as a tandem catalyst completely reduced tribromophenol with high phenol selectivity. The intrinsic catalytic activity of Pd and Cu in PdCu SAA substantially outperforms their monometallic counterparts by 14.4 and 3.2 times, respectively. This work showcases that the atomic dispersion of noble metals in SAA offers a promising catalyst design strategy to attain unprecedented catalytic properties via isolating activation and desorption steps.

Atomic Pd catalysis Cu nanosheets Electrochemical dehalogenation Hydrogen spillover Tribromophenol

SCI ; EI

英语

通讯

National Natural Science Foundation of China["22005288","22176131"] ; Key Project of Basic Research of Shenzhen[JCYJ20220818095601002]

Chemistry ; Engineering

Chemistry, Physical ; Engineering, Environmental ; Engineering, Chemical

WOS:001005458200001

ELSEVIER

20230913632023

Atoms ; Binary alloys ; Catalyst activity ; Catalyst selectivity ; Catalyst supports ; Copper ; Crystal atomic structure ; Dispersions ; Electronic structure ; Gas adsorption ; Kinetic energy ; Kinetics ; Nanosheets ; Palladium ; Palladium alloys ; Single crystals

Copper:544.1 ; Precious Metals:547.1 ; Fluid Flow, General:631.1 ; Nanotechnology:761 ; Chemical Reactions:802.2 ; Chemical Operations:802.3 ; Chemical Agents and Basic Industrial Chemicals:803 ; Chemical Products Generally:804 ; Classical Physics; Quantum Theory; Relativity:931 ; Atomic and Molecular Physics:931.3 ; Solid State Physics:933 ; Crystalline Solids:933.1 ; Crystal Lattice:933.1.1 ; Materials Science:951

CHEMISTRY

2-s2.0-85148640994

Scopus

1.College of Chemistry and Environmental Engineering,Shenzhen University,Shenzhen,518060,China
2.Department of Materials Science and Engineering,Southern University of Science and Technology,Shenzhen,518055,China
3.Hefei National Laboratory for Physical Sciences at the Microscale,University of Science and Technology of China,Hefei,230026,China
4.Departments of Chemical and Petroleum Engineering,University of Wyoming,82071,United States
5.School of Chemical Engineering,The University of Queensland,Brisbane,4072,Australia

Chen，Huihuang,Li，Hongbo,Chen，Shaoqing,et al. Atomic Pd dispersion in triangular Cu nanosheets with dominant (111) plane as a tandem catalyst for highly efficient and selective electrodehalogenation[J]. APPLIED CATALYSIS B-ENVIRONMENTAL,2023,328.

Chen，Huihuang.,Li，Hongbo.,Chen，Shaoqing.,Sheng，Li.,Zhang，Zhirong.,...&Yang，Bo.(2023).Atomic Pd dispersion in triangular Cu nanosheets with dominant (111) plane as a tandem catalyst for highly efficient and selective electrodehalogenation.APPLIED CATALYSIS B-ENVIRONMENTAL,328.

Chen，Huihuang,et al."Atomic Pd dispersion in triangular Cu nanosheets with dominant (111) plane as a tandem catalyst for highly efficient and selective electrodehalogenation".APPLIED CATALYSIS B-ENVIRONMENTAL 328(2023).