cMOF Evidence Base
Electrochemistry Application — Selective reduction of CO2 by conductive MOF nanosheets as an efficient co-catalyst under visible light illumination

Measurement evidence

Electrochemistry Application

Selective reduction of CO2 by conductive MOF nanosheets as an efficient co-catalyst under visible light illumination · Zhu W., Zhang C., Li Q. et al. · Applied Catalysis B: Environmental · 2018 · 339-345

10 measurement groups · 35 results

Reported values remain attached to the sample, method, conditions, extraction quality and source location that produced them.

Three-electrode LSV and online GC product analysis

Voltammetry

Ni3(HITP)2/carbon black/Nafion carbon-paper electrode · Electrode

H-cell separated by Nafion 117; Ag/AgCl reference; graphite counter electrode; CO2-saturated 0.5 M KHCO3; scan rate 1 mV/s; products analysed by Agilent 7890B GC-TCD/FID.

Atmosphere
CO2-saturated electrolyte
Geometry
1 cm2 carbon-paper working electrode with Ni3(HITP)2/carbon black/Nafion ink
Context
composite electrode containing pristine Ni3(HITP)2
Measurement source
main p.3, article p.341 · 2.5. Electrochemical measurements · Figure S12
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
Electrolysis gas selectivity over potential rangeonly CO and no H2 over -0.32 V to -0.72 V vs RHE——Text
Qualitative		main p.6, article p.344 · Results and discussion · Figure S12b
CO product at -0.72 V vs RHEabout 350 ppm CO, no H2 detected——Figure Axis
Approximate		SI rendered p.9 · Supporting Information · Figure S12b
Current density at -0.8 V vs RHEabout 12 mA cm-2 at -0.8 V vs RHE120 A m-2—Text
Approximate		main p.6, article p.344 · Results and discussion · Figure S12a
Electrocatalytic CO2 reduction onset potentialabout -0.3 V vs RHE——Text
Approximate		main p.5, article p.343 · Results and discussion · Figure S12

Visible-light photocatalytic CO2 reduction using unexfoliated bulk Ni3(HITP)2 control

Bulk Ni3(HITP)2/[Ru(bpy)3]2+ photocatalytic control mixture · Powder

2 mg bulk Ni3(HITP)2 powder substituted for nanosheets in the same MeCN/H2O/TEOA, [Ru(bpy)3]2+, CO2 and LED system.

Temperature
277
Atmosphere
CO2
Geometry
external irradiation photoreactor
Context
hybrid application mixture containing pristine bulk Ni3(HITP)2
Measurement source
main p.6, article p.344 · Figure S15
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
Bulk Ni3(HITP)2 control CO yield rate2.87 x 10^4 umol g-1 h-128.7 mmol g-1 h-1—Text
Exact Reported		main p.6, article p.344 · Results and discussion · Figure S15
Bulk Ni3(HITP)2 CO produced after 3 habout 172 umol CO after 3 h——Calculated From Reported
Approximate		main p.6, article p.344 · Results and discussion · Figure S15

Photocatalytic control experiments with gases analysed by GC

Photocatalytic control mixtures lacking one active component · Unknown

Controls include no Ni3(HITP)2, no photosensitiser, no irradiation, no CO2, Ni2+ ions and ligand controls under comparable photocatalytic conditions.

Temperature
277
Atmosphere
varies by control; CO2 absent in one control
Geometry
external irradiation photoreactor
Context
controls lacking the complete conductive MOF framework or one operating condition
Measurement source
main p.5, article p.343 · Results and discussion · Figures S10 and S11
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
HATP ligand control CO productabout 15 umol CO at 3 h——Figure Axis
Approximate		SI rendered p.8 · Supporting Information · Figure S10
NiCl2 control CO productabout 15 umol CO at 3 h——Figure Axis
Approximate		SI rendered p.8 · Supporting Information · Figure S10
Ni2+ ion and ligand controlsnegligible performance——Text
Qualitative		main p.5, article p.343 · Results and discussion · Figure S10
No CO2 control H2 productH2 14 umol; no CO——Text
Exact Reported		main p.6, article p.344 · Results and discussion · Figure S10/S11
No irradiation control productsno detectable CO and H2——Text
Qualitative		main p.6, article p.344 · Results and discussion · Figure S10/S11
CO produced without Ni3(HITP)212 umol CO in 3 h——Text
Exact Reported		main p.5, article p.343 · Results and discussion · Figure S10
H2 produced without Ni3(HITP)27.46 umol H2 in 3 h——Text
Exact Reported		main p.5, article p.343 · Results and discussion · Figure S11
No photosensitiser control productsneither CO nor H2 detected——Text
Qualitative		main p.6, article p.344 · Results and discussion · Figure S10/S11

Visible-light photocatalytic CO2 reduction with online gas chromatography and 1H NMR liquid-product analysis

Nuclear magnetic resonance

Ni3(HITP)2 nanosheet/[Ru(bpy)3]Cl2.6H2O photocatalytic mixture · Unknown

2 mg Ni3(HITP)2, 80 mg [Ru(bpy)3]Cl2.6H2O, 16 mL MeCN/H2O/TEOA 10:2:4 v/v/v, 80 kPa CO2, 4 C, 100 W LED at 420 nm, 7.5 cm illumination distance; gases analysed hourly by GC-TCD/FID.

Temperature
277
Atmosphere
80 kPa CO2
Geometry
external irradiation Pyrex reactor with quartz window and closed gas-circulation system
Context
hybrid application mixture containing pristine Ni3(HITP)2 nanosheets
Measurement source
main p.3, article p.341 · 2.4. Photocatalytic activity evaluation · Fig. 3a
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
CO produced after 3 habout 207 umol CO within 3 h——Text
Approximate		main p.4, article p.342 · Results and discussion · Fig. 3a
CO produced after extended 5 h reaction274 umol after 5 h——Text
Rounded Reported		main p.4, article p.342 · Results and discussion · Figure S7
CO yield rate for nanosheetsMarked as a best value within this paper3.45 x 10^4 umol g-1 h-134.5 mmol g-1 h-1—Text
Exact Reported		main p.4, article p.342 · Results and discussion · Fig. 3a
CO selectivityMarked as a best value within this paper97%0.97 fraction—Text
Exact Reported		main p.1, article p.339 · Abstract
H2 produced after 3 h7.49 umol H2 within 3 h——Text
Exact Reported		main p.4, article p.342 · Results and discussion · Fig. 3a
Liquid product screenno soluble products such as formate found by 1H NMR——Text
Qualitative		main p.4, article p.342 · Results and discussion · Figure S4

Photocatalytic recycling stability test

Ni3(HITP)2 nanosheet/[Ru(bpy)3]Cl2.6H2O photocatalytic mixture · Unknown

Partition method using 2 mg MOF catalyst from a total 20 mg; catalysts mixed, washed, centrifuged and dried between cycles; six consecutive cycles under the same photocatalytic conditions.

Temperature
277
Atmosphere
80 kPa CO2
Geometry
external irradiation photoreactor
Context
hybrid application mixture containing pristine Ni3(HITP)2 nanosheets
Measurement source
main p.3, article p.341 · 2.4. Photocatalytic activity evaluation · Fig. 3b
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
Consecutive photocatalytic cycles6 consecutive cycles with no sign of performance decay——Text
Exact Reported		main p.4, article p.342 · Results and discussion · Fig. 3b, Figures S8 and S9

Extended 7 h photocatalytic CO time course

Ni3(HITP)2 nanosheet/[Ru(bpy)3]Cl2.6H2O photocatalytic mixture · Unknown

Standard 2 mg Ni3(HITP)2/80 mg [Ru(bpy)3]Cl2.6H2O photocatalytic system monitored for 7 h; CO read from Figure S7.

Atmosphere
CO2
Geometry
photoreactor
Context
hybrid application mixture containing pristine Ni3(HITP)2 nanosheets
Measurement source
SI rendered p.7 · Supporting Information · Figure S7
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
CO produced after 7 h extended irradiationabout 274 umol CO at 7 h plateau——Figure Axis
Approximate		SI rendered p.7 · Supporting Information · Figure S7

Photocatalytic CO evolution versus Ni3(HITP)2 loading

Ni3(HITP)2 nanosheet/[Ru(bpy)3]Cl2.6H2O photocatalytic mixture · Unknown

MeCN/H2O/TEOA solution, 80 mg [Ru(bpy)3]Cl2.6H2O and different Ni3(HITP)2 amounts; CO evolution over 3 h read from Figure S5.

Temperature
277
Atmosphere
CO2
Geometry
photoreactor
Context
hybrid application mixture varying pristine Ni3(HITP)2 amount
Measurement source
SI rendered p.6 · Supporting Information · Figure S5
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
CO at 3 h with 1 mg Ni3(HITP)2about 95 umol CO at 3 h——Figure Axis
Approximate		SI rendered p.6 · Supporting Information · Figure S5
CO at 3 h with 3 mg Ni3(HITP)2about 235 umol CO at 3 h——Figure Axis
Approximate		SI rendered p.6 · Supporting Information · Figure S5

Photocatalytic CO evolution versus [Ru(bpy)3]2+ loading

Ni3(HITP)2 nanosheet/[Ru(bpy)3]Cl2.6H2O photocatalytic mixture · Unknown

MeCN/H2O/TEOA solution containing 2 mg Ni3(HITP)2 and different [Ru(bpy)3]Cl2.6H2O amounts; CO evolution over 3 h read from Figure S6.

Temperature
277
Atmosphere
CO2
Geometry
photoreactor
Context
hybrid application mixture varying photosensitiser amount
Measurement source
SI rendered p.6 · Supporting Information · Figure S6
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
CO at 3 h with 20 mg [Ru(bpy)3]Cl2.6H2Oabout 90 umol CO at 3 h——Figure Axis
Approximate		SI rendered p.6 · Supporting Information · Figure S6
CO at 3 h with 40 mg [Ru(bpy)3]Cl2.6H2Oabout 150 umol CO at 3 h——Figure Axis
Approximate		SI rendered p.6 · Supporting Information · Figure S6
CO at 3 h with 60 mg [Ru(bpy)3]Cl2.6H2Oabout 185 umol CO at 3 h——Figure Axis
Approximate		SI rendered p.6 · Supporting Information · Figure S6
CO at 3 h with 80 mg [Ru(bpy)3]Cl2.6H2Oabout 207 umol CO at 3 h——Figure Axis
Approximate		SI rendered p.6 · Supporting Information · Figure S6

Quantum efficiency and turnover-frequency calculation

Ni3(HITP)2 nanosheet/[Ru(bpy)3]Cl2.6H2O photocatalytic mixture · Unknown

SI calculation using 608 W/m2 light intensity, 19.6 cm2 illuminated area, 420 nm wavelength, 3 h irradiation, 207 umol CO and 2.5 umol catalyst amount.

Geometry
calculation
Context
hybrid application mixture containing pristine Ni3(HITP)2 nanosheets
Measurement source
SI rendered p.2 · Calculations · Calculations
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
Illuminated petri-dish area19.6 cm20.00196 m2—Text
Exact Reported		SI rendered p.2 · Calculations · Calculations
LED irradiation intensity for QE calculation608 W m-2——Text
Exact Reported		SI rendered p.2 · Calculations · Calculations
Incident photons in 3 h2.7 x 10^22 photons——Text
Rounded Reported		SI rendered p.2 · Calculations · Calculations
Overall quantum efficiencyMarked as a best value within this paper0.92%0.0092 fraction—Text
Exact Reported		SI rendered p.2 · Calculations · Calculations
Turnover frequencyMarked as a best value within this paper7.7 x 10^-3 s-1——Text
Exact Reported		SI rendered p.2 · Calculations · Calculations

SI Table S1 benchmark comparison

Ni3(HITP)2 nanosheet/[Ru(bpy)3]Cl2.6H2O photocatalytic mixture · Unknown

Reported co-catalyst comparison table for photocatalytic CO2 reduction to CO.

Context
hybrid application mixture containing pristine Ni3(HITP)2 nanosheets
Measurement source
SI rendered p.3 · Table S1 · Table S1
PropertyReported valueNormalised valueUncertaintyOrigin and qualitySource
Table S1 this-work CO evolution rate69 umol h-1——SI Table
Exact Reported		SI rendered p.3 · Table S1 · Table S1
Table S1 this-work QE0.92%0.0092 fraction—SI Table
Exact Reported		SI rendered p.3 · Table S1 · Table S1