A Presentation on paper titled:
TOWARD BIOMASS-BASED SINGLE-ATOM CATALYSTS
AND PLASTICS:
HIGHLY ACTIVE SINGLE-ATOM CO ON N-DOPED
CARBON FOR OXIDATIVE ESTERIFICATION OF PRIMARY
ALCOHOLS
Hua Zhoua, Song Hongb, Hao Zhangc, Yongting Chene, Huanghui Xua , Xueke
Wanga , Zheng Jiangc, Shengli Chene,Yun Liua
Applied Catalysis B: Environmental. 256. 117767.9(2019)
10.1016/j.apcatb.2019.117767.
BY:
Satyam Pandey
CH22MTECH14006
SINGLE ATOM CATALYSTS(SAC)
• Isolated metal atoms singly dispersed on support.
Why SAC?
Traditional NPs have mix of sizes in
clusters causing heterogeneity.
Decreased metal atom efficiency.
Undesirable side rxn.
No identification of active sites.
Ref. Cobalt Compounds and Applications, Baljeet Singh
SINGLE ATOM CATALYSTS
• Merits:
• Efficient atom use
• High selectivity & activity
• Durability
Xiao-Feng Yang, et. al(ACS 2013)
Demerits:
• Possibility of metal
particle aggregation
• Large scale fabrication
PAPER SPECIFIC
APPLICATION
• To synthesize highly active SAC of Co on N-doped C for
oxidative esterification of primary alcohols:
• HMF and furfural are converted into valued esters by lignin-based Co
SAs-N@C catalyst.
Ref.Aerobic
Oxidation of
Hydroxymethylfu
rfural and
Furfural by Using
Heterogeneous
CoxOy–N@C
Catalysts
Jian Deng et al
Nomenclature:
M-SAs-N@C
Metal
Atom N doped
Fe,Cu,Ni, Single Atom(s) on Carbon
Co
CATALYST
PREPARATION
Approach: WET CHEMISTRY (Wei Liu et al)
Traditional Approach:
Improvised Approach(Organometallic Compounds):
Organometallic Chemistry Meets Surface Science,Pedro Serna Accounts of Chemical Research 2014
8g Lignin+ 1L
deionised water
Mech. Stirring
SYNTHESIS
OF Black Lignin Soln.
+
Co SAs-N@C Co(NO3)2.6H2O (8 mmol) and
Zn(NO3)2.6H2O (40 mmol)
Stir 1 hr followed by12h ageing
drying@80 ℃ ¢rifugation
Co/Zn-L complex
+10x
dicyandiamide
Zn: Increases spatial Mixture Powder
distance of targeted metal Annealing @550℃ 1h
ion +@1000 ℃ 1h
Dicyandiamine: N- source Co SAs-N@C catalyst
after cooling ready for
characterisation
CATALYST
CHARACTERISATION
• TEM & HAADF-
STEM:
High Angle Annular
Collects and samples e- from Dark Field –Scanning
annulus around beam, giving Transmission Electron
high efficiency and brighter Microscopy
image.
Results:
Confirms that isolated Co
atoms are homogenously
dispersed on C support.
HAADF-STEM images reveal
the atomic dispersion of metal
atoms in M SAs-N@C
catalysts
CATALYST
CHARACTERISATION Co2p XPS spectrum of
Co SAs-N@C
XPS, XANES &
EXAFS:
B.E of Co2p peak in Co
SAs-N@C is 780.5eV
CoIII > Co SAs-N@C > CoII
781eV 780.5eV 779.2eV
Peak of Co SAs-N@C in XANES
intermediate of CoO and Co3O4
Oxidation state of Co within Co SAs-N@C
is between +2 and +3.
Electronic structure identified by XANES XANES spectra
and EXAFS
CATALYST
EXAFS: CHARACTERISATION
• Provides info around local structure
within 0.5nm.
• Reveals that Co atoms are isolated and
predominantly coordinated with N
and/or C atoms in Co SAs-N@C.
• Curve fitting of EXAFS data reveals
coordination no. of 1.0 for C and 2.9 for
N
N: coordination
numbers;
R: the internal
atomic distance
ΔE0:the edge-
energy shift
CATALYTIC PERFORMANCE
• Only non noble catalyst exhibiting
activity for oxidative esterification.
• Gives highest TOF of 55.6 h-1
• Outperforms other state of art metal
heterogenous catalysts.
Can easily be recycled from rxn. by
filtration; 99.8% conversion of fresh batch
after 5 cycles.
CONCLUSIONS
• SAC catalysts outperform conventional metal heterogenous and NPs catalysts.
• Organometallic complex approach of WET CHEMISTRY catalyst preparation
avoids metal aggregation and is a good biomass based SAC.
• Catalyst characterisation techniques like XPS,TEM, HAADF-
STEM,XANES,EXAFS reveal electronic structure, BE, oxidation states,
neighbouring conditions of Co atoms.
• Co SAs-N@C SAC is a good performing catalyst for oxidative esterification of
alcohols, finding application in conversion of carbohydrate derived furans to
fragrancing compounds which form the base for bioplastics.
