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University of Nottingham activities
Focus on capacity building.
ASGARD facility for investigating CO2 release.
Is CHn -> C + n/2H2 a feasible route for carbon
sequestration and hydrogen production (catalytic cracking of hydrocarbons gases)?
Long-term CO2 utilisation - efficient catalysts
for photocatalytic CO2 reduction.
Artificial Soil Gassing And Response Detection
Mike Steven, Jeremy Colls & Karon SmithUniversity of Nottingham
Schools of Geography (MS) and Biosciences (JC&KS)
ASGARD
Co-funding from SRIF3 allowed the development of a “permanent” field experimental facility - ASGARD
The TSEC programme (UKCCSC) funded 13 months effort to establish and test ASGARD and to run one field season.
The ASGARD facility
Gas injection
Gas monitoring
Gas response
Gas store
Gas control
ASGARD Site layout 2006
GRASS
LINSEED
BARLEY
TES
T
N
rc
• Plots 2.5 m square• 8 plots of grass, linseed &
barley• 4 Gassed and 4 control
plots
• Gas injected at 0.6 m depth
• Plus 4 “remote” controls for grass (rc)
rc
ASGARD: achievements and plans
From TSEC study
• We can control CO2 release rates and soil concentrations.
• We can relate soil CO2 concentrations to fluxes into the atmosphere.
• We can detect CO2 induced stress effects in plants at soil concentrations of a few percent by remote sensing techniques.
• We can discriminate fossil and biogenic carbon by isotopic analysis.
Ongoing and future work
• Responses of plant root systems and effects on competition
• Stress sensitivities of different plant species determined by spectral responses
• Soil and soil water chemistry
• Effects of SO2 contamination in leaked CO2
• CO2 pathways in soil
• Ecosystem recovery after gassing
Is CHn -> C + n/2H2 a feasible route for carbon sequestration and hydrogen
production?
Colin Snape, Miguel Castro Diaz and Jamie Blackman
Catalytic cracking of hydrocarbon gases gives carbon nanofibres (CNFs).
Driven by the value and utility of the carbon.
CNFs – poor for hydrogen storage but OK as adsorbents
Building sector – cement and bricks combined account for ca. 5% global CO2 emissions.
Replacing existing building materials begins to look attractive as am means of avoiding CO2 emissions.
Still attractive if the yield of hydrogen is not that high (e.g. for coal cf. CH4).
Catalytic decomposition of methane over supported metal catalysts has been widely studied in recent years to produce hydrogen free of CO and CO2.
The highest amount of hydrogen per metal has been obtained with a Pd-Ni/CNF catalyst (ca. 16,000 molC/molPd+Ni) after 30 hours [1].
The challenge is to achieve these high conversions with lower cost catalysts (i.e. base metals).
An unsupported Ni-Cu (4:1 wt/wt) metal alloy catalyst has been studied for the catalytic decomposition of ethene at 650-700°C.
Hydrogen production via catalytic cracking of hydrocarbons
[1] Takenaka et al., Journal of Catalysis 220 (2003) 468-477.
Configuration
Pure C2H4 (60 ml min-1) was decomposed over 25-100 mg of catalyst precursor in a quartz tube reactor for 3-9 hours.
Hydrogen production via catalytic cracking
High H2 selectivities (>75%) and C2H4 conversions (>90%) were achieved before catalyst deactivation.
High yields of ca. 4,500 molC/mol(Cu+Ni) were achieved after 9 hours of reaction at 650oC.
CNFs produced at 650oC cf. amorphous carbon at 700oC.
Test 1 : 60ml/min at 650°C
0
10
20
30
40
50
60
70
80
90
100
0 50 100 150 200
Time (min)
Gas c
om
po
sitio
n (%
)
CH4 C2H4
C2H6 H2
Hydrogen production via catalytic cracking
Although the conversion of CH4 is thermodynamically less favourable, unsupported Ni-Cu alloy catalysts could provide high conversions because of their high activity at higher temperatures (i.e. 700°C).
Applied Catalysis paper in press.
Further avenues for support are being explored to take the concept forward, especially for carbons in buildings (Halloran paper).
Long Term CO2 Utilisation (M. W. George - Nottingham)
1-Year PDRA Aims:
• To develop efficient catalysts for photocatalytic CO2 reduction
• To develop viable catalysts via understanding catalytic mechanism
• Explore the use of supercritical CO2 (scCO2)
– a solvent with several advantages including
(i) highest possible concentration of CO2
(ii) improved mass transport and high diffusivity
(iii) opportunities for efficient recovery of products
CO2 Reduction If Nature Can Do It, Why Can't We?
Strategy for CO2 Reduction
Reduction of CO2 requires energy Photon as energy source (Photochem)
Electricity as energy source (Electrochem)
Artificial photosynthesis for CO2 reduction typically requires:
photosensitizer, catalyst electron donor
Products are CO, formate, and H2
Co macrocycles
Ni macrocycles
Cobalt and Iron porphyrins,
Phthalocyanines and corroles
Ru(bpy)2(CO)X
Re(bpy)(CO)3X
Ni(bpy)32+
Re
N
NCl
CO
CO
CO
Re
N
NCl
CO
CO
CO
+-
Re
N
NCl
CO
CO
CO
-
charge separation
h
TEA
TEA+
Key Achievements:
• Strategic Alliance and Collaboration with leaders at Brookhaven National Laboratory (Fujita) in Photocatalytic CO2 reduction to develop catalysts for CO reduction in scCO2
• The promise of this new approach to CO2 reduction was picked up by the popular press and made front cover of CE&E news – key publication the American Chemical Society
• Development of catalyst which was soluble in scCO2
• Kinetic studies of mechanisms from picosecond (10-12 s) to seconds Mechanistic Studies to understand factors which affect solvent control of the catalytic cycle
• Monitoring, for the first time, rate of Cl- from key catalytic intermediate providing the understanding how to design and develop viable new catalytic systems
2100 2050 2000 1950 1900 1850
0.00
0.04
0.08
0.12
0.16
Wavenumber/ cm-1
FTIR
-6
-4
-2
0
2
4
6
300 ns
2020
2007
1901
1920
2025
2063
1.4 ns
-6
-4
-2
0
2
4
6
-6
-4
-2
0
2
4
6 1.4ns 2ns 2.9ns 4.1ns 5.9ns 8.4ns 12ns 50ns 300ns
A
bso
rba
nce
x 1
0-3
-5 0 5 10 15 20 25 30 35 40 45 50
0.0000
0.0005
0.0010
0.0015
0.0020 MLCT Data: Kineticdata_2063.82605Model: ExpDec1Equation: y = A1*exp(-x/t1) + y0Weighting: y No weighting Chi^2/DoF = 3.0237E-9R^2 = 0.99301 y0 -2.9572E-6 ±0.00001A1 0.00315 ±0.00011t1 2.44783 ±0.1248
Time ns
20
63
cm-1
0.0000
0.0005
0.0010
0.0015
0.0020
= 1ns
20
07
cm-1
A
bso
rba
nce
= 2ns
= 5ns
Phenazine
Data: Kineticdata_2007.12965Model: ExpDec2Equation: y = A1*exp(-x/t1) + A2*exp(-x/t2) + y0Weighting: y No weighting Chi^2/DoF = 2.5457E-9R^2 = 0.99191 y0 0.00025 ±0.00001A1 -0.00242 ±0.00017t1 0.64328 ±0.08106A2 0.00207 ±0.00016t2 5.07996 ±0.45935
Phen
Kinteic traces
-0.001
0.000
0.001
0.002
0.003
Data: Kineticdata_2023.00824Model: ExpDec1Equation: y = A1*exp(-x/t1) + y0Weighting: y No weighting Chi^2/DoF = 1.7941E-8R^2 = 0.9852 y0 0.00256 ±0.00004A1 -0.00426 ±0.00019t1 5.04402 ±0.39287
20
23
cm-1
= 5ns
A few nanosecondsA few seconds
•1-Year funding developed science which resulted in being invited to join a consortium with UEA (Pickett/Nann); York (Perutz); Manchester (Flavell) to develop a new approach to artificial photosynthesis which was recently funded (ca. £1.5 M - £300 k to Nottingham) under EPSRC Solar Energy Initiative
Carbon Dioxide and Alkanes as Electron-sink and Source in a Solar Nanocell: towards Tandem Photosynthesis of Carbon Monoxide and
Methanol
•This proposal exploits the knowledge gained out of this one year funding.
Long Term CO2 Utilisation – future work