PMID- 31464326
OWN - NLM
STAT- PubMed-not-MEDLINE
LR  - 20190830
IS  - 2040-3372 (Electronic)
IS  - 2040-3364 (Linking)
VI  - 11
IP  - 34
DP  - 2019 Aug 29
TI  - Identifying the rate-determining step of the electrocatalytic hydrodechlorination 
      reaction on palladium nanoparticles.
PG  - 15892-15899
LID - 10.1039/c9nr04634h [doi]
AB  - Identifying the rate-determining step over the catalysts and clarifying the 
      underlying mechanisms are crucial for maximizing the electrocatalytic 
      hydrodechlorination (EHDC) efficiency for detoxification of the chlorophenol 
      pollutants in water. Here, monodisperse palladium nanoparticles (Pd NPs) 
      separately supported on carbon (C) and titanium nitride (TiN) were synthesized as 
      two model catalysts. The support effects on EHDC efficiency, kinetics and current 
      efficiency towards 2,4-dichlorophenol (2,4-DCP), and the electronic structure of 
      Pd and its binding strengths with 2,4-DCP, phenol and Cl- (the primary EHDC 
      product) were investigated by experimental and density functional theory (DFT) 
      analyses. The low current efficiency (<30%) of both catalysts and the good 
      description of EHDC kinetics by the Langmuir-Hinshelwood model suggest that the 
      2,4-DCP coverage on Pd, rather than the well-known adsorbed hydrogen generation, 
      determines EHDC efficiency. Furthermore, the superior EHDC efficiency on TiN-Pd 
      (96.4% vs. 80.9% on C-Pd), coupled with the weakened adsorption of 2,4-DCP and 
      phenol on TiN-supported Pd, demonstrates that the 2,4-DCP coverage is largely 
      influenced by phenol due to its poisoning effect by blocking active sites, and 
      phenol desorption is the rate-determining step of EHDC on the catalyst. The 
      support TiN enables alleviation of the phenol poisoning by modulating the 
      electronic structure of Pd. The d band center of Pd can serve as a potential 
      descriptor of EHDC efficiency, and its optimization for balancing 2,4-DCP and 
      phenol adsorption should be an effective strategy to enhance EHDC.
FAU - Fu, Wenyang
AU  - Fu W
AD  - Engineering Research Center for Waste Oil Recovery Technology and Equipment, 
      Ministry of Education, Chongqing Technology and Business University, Chongqing 
      400067, China. jiangguangming@zju.edu.cn.
FAU - Shu, Song
AU  - Shu S
FAU - Li, Junxi
AU  - Li J
FAU - Shi, Xuelin
AU  - Shi X
FAU - Lv, Xiaoshu
AU  - Lv X
FAU - Huang, Yu-Xi
AU  - Huang YX
FAU - Dong, Fan
AU  - Dong F
FAU - Jiang, Guangming
AU  - Jiang G
LA  - eng
PT  - Journal Article
PL  - England
TA  - Nanoscale
JT  - Nanoscale
JID - 101525249
SB  - IM
EDAT- 2019/08/30 06:00
MHDA- 2019/08/30 06:01
CRDT- 2019/08/30 06:00
PHST- 2019/08/30 06:00 [entrez]
PHST- 2019/08/30 06:00 [pubmed]
PHST- 2019/08/30 06:01 [medline]
AID - 10.1039/c9nr04634h [doi]
PST - ppublish
SO  - Nanoscale. 2019 Aug 29;11(34):15892-15899. doi: 10.1039/c9nr04634h.