Electrochemistry Application — Decoupling Redox Hopping and Catalysis in Metal-Organic Frameworks -based Electrocatalytic CO2 Reduction

5 measurement groups · 34 results

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

constant-potential electrolysis with gas chromatography product analysis

CoPc@NU-1000-h carbon/Nafion electrode · Electrode

H-cell, 0.5 M KHCO3(aq), CO2 purge 15 min, products analysed by GC-TCD

Atmosphere: CO2
Geometry: three-electrode H-cell separated by Nafion membrane
Context: MOF electrode with carbon black and Nafion
Measurement source: 5 · Heterogeneous electrochemical experiments · Figures 6, S15, S18-S19

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Faradaic efficiency to CO for CoPc@NU-1000-hMarked as a best value within this paper	FECO reaching 80% at -0.65 V vs RHE	—	—	Text Rounded Reported	4 · Results and Discussion · Figure 6a
Faradaic efficiency to CO for CoPc@NU-1000-l	75% at -0.65 V vs RHE; also discussed as 74%	—	—	Text Rounded Reported	4 · Results and Discussion · Figure S18
Faradaic efficiency to CO for TPP(Co)@NU-1000 at -0.75 V	FECO = 24% at -0.75 V	—	—	Text Exact Reported	4 · Results and Discussion · Figure 6a
Faradaic efficiency to CO for TPP(Co)@NU-1000 at -1.30 V	7.0% at -1.30 V	—	—	Text Exact Reported	4 · Results and Discussion · Figure 6a
Faradaic efficiency to CO for TPP(Co)@NU-1000 in 0.1 M KHCO3	FECO = 31% in 0.1 M KHCO3	—	—	Text Exact Reported	5 · Results and Discussion
Faradaic efficiency to H2 for TPP(Co)@NU-1000 at -1.30 V	FEH2 = 72.4% at -1.30 V	—	—	Text Exact Reported	4 · Results and Discussion · Figure 6a
H2 production after 2 h for CoPc@NU-1000-h	approximately 11 umol from Figure S19	—	visual estimate	Visual Estimate Approximate	14 · Electrochemistry · Figure S19
H2 production after 2 h for CoPc@NU-1000-l	approximately 4.3 umol from Figure S19	—	visual estimate	Visual Estimate Approximate	14 · Electrochemistry · Figure S19
H2 production after 2 h for pristine NU-1000 electrode	approximately 7.7 umol from Figure S19	—	visual estimate	Visual Estimate Approximate	14 · Electrochemistry · Figure S19
H2 production after 2 h for TPP(Co)@NU-1000	approximately 7.0 umol from Figure S19	—	visual estimate	Visual Estimate Approximate	14 · Electrochemistry · Figure S19
partial current density for CO on CoPc@NU-1000-hMarked as a best value within this paper	JCO = 1.22 mA cm-2	—	—	Text Exact Reported	5 · Results and Discussion · Figure 6b
partial current density for CO on CoPc@NU-1000-l	JCO = 0.49 mA cm-2	—	—	Text Exact Reported	5 · Results and Discussion · Figure 6b
partial current density for CO on TPP(Co)@NU-1000	about 0.07 mA cm-2, inferred because CoPc@NU-1000-h and -l are 17x and 7x higher	—	about	Calculated From Reported Approximate	5 · Results and Discussion · Figure 6b
partial current density for H2 on CoPc@NU-1000-h	approximately 0.28 mA cm-2 from Figure 6b	—	visual estimate	Visual Estimate Approximate	4 · Results and Discussion · Figure 6b
partial current density for H2 on CoPc@NU-1000-l	approximately 0.12 mA cm-2 from Figure 6b	—	visual estimate	Visual Estimate Approximate	4 · Results and Discussion · Figure 6b
partial current density for H2 on TPP(Co)@NU-1000	approximately 0.15 mA cm-2 from Figure 6b	—	visual estimate	Visual Estimate Approximate	4 · Results and Discussion · Figure 6b
turnover number for CO after 4 h on CoPc@NU-1000-hMarked as a best value within this paper	approximately 470 after 4 h from Figure 6c	—	visual estimate	Visual Estimate Approximate	4 · Results and Discussion · Figure 6c
turnover number for CO after 4 h on CoPc@NU-1000-l	approximately 305 after 4 h from Figure 6c	—	visual estimate	Visual Estimate Approximate	4 · Results and Discussion · Figure 6c
turnover number for CO after 4 h on TPP(Co)@NU-1000	TON = 35 in 4 hours	—	—	Text Exact Reported	5 · Results and Discussion · Figure 6c

homogeneous cyclic voltammetry

Voltammetry

CoPc-COOH · Powder

0.5 mM CoPc or TPP(Co) in 5 mL DMF with 0.1 M TBAPF6; glassy carbon working electrode

Atmosphere: Ar and CO2
Geometry: glassy carbon electrode
Context: molecular precursor comparison
Measurement source: 5 · Homogeneous electrochemical experiments · Figure S9

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
CoPc Co(II/I) redox potential	0.39 V vs RHE	—	—	Text Rounded Reported	4 · Results and Discussion · Figure 5
CoPc Co(I/0) redox potential	ca -0.35 V vs RHE	—	ca	Text Approximate	4 · Results and Discussion · Figure 5
NU-1000 TBAPy-centred reduction potential	-0.32 V vs RHE	—	—	Text Rounded Reported	4 · Results and Discussion · Figure 5
TPP(Co) Co(II/I) redox potential	-0.11 V vs RHE	—	—	Text Rounded Reported	4 · Results and Discussion · Figure 5
TPP(Co) Co(I/0) redox potential	-1.23 V vs RHE	—	—	Text Rounded Reported	4 · Results and Discussion · Figure 5

linear sweep voltammetry and first derivative analysis

Voltammetry

CoPc@NU-1000-h carbon/Nafion electrode · Electrode

MOF catalyst plus Nafion on graphite sheet; 0.5 M KHCO3(aq); CO2 and argon atmospheres; carbon black omitted for onset determination

Atmosphere: CO2 and Ar
Geometry: graphite sheet working electrode
Context: application electrode, no carbon black for Figure 4 onset
Measurement source: 3 · Results and Discussion · Figure 4

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
e-CRR onset potential for CoPc@NU-1000-hMarked as a best value within this paper	-0.42 V vs RHE	—	—	Figure Axis Rounded Reported	3 · Results and Discussion · Figure 4b
e-CRR onset potential for CoPc@NU-1000-l	-0.42 V vs RHE	—	—	Figure Axis Rounded Reported	11 · Electrochemistry · Figure S12
e-CRR onset potential for TPP(Co)@NU-1000	-0.82 V vs RHE	—	—	Figure Axis Rounded Reported	3 · Results and Discussion · Figure 4c

scan-rate dependent cyclic voltammetry

Voltammetry

CoPc@NU-1000-h carbon/Nafion electrode · Electrode

Non-faradaic region at varied scan rates; catalyst/carbon black/Nafion on graphite sheet; 0.5 M KHCO3 under CO2

Atmosphere: CO2
Geometry: graphite sheet working electrode
Context: MOF electrode with carbon black and Nafion
Measurement source: 11 · Electrochemistry · Figures S11-S14

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
double-layer capacitance from scan-rate CV for CoPc@NU-1000-h	0.86 mF	—	—	Text Exact Reported	5 · Results and Discussion · Figure S11
double-layer capacitance from scan-rate CV for TPP(Co)@NU-1000	0.6 mF	—	—	Text Exact Reported	5 · Results and Discussion · Figure S11

post-electrolysis UV-vis, CV, PXRD, DRIFTS, and TEM-EDS stability checks

Infrared spectroscopy UV-visible and optical absorption spectroscopy X-ray diffraction and scattering Transmission electron microscopy Elemental microanalysis and mapping Voltammetry

CoPc@NU-1000-h carbon/Nafion electrode · Electrode

CoPc@NU-1000-h electrode after 2 h to 4 h e-CRR; digestion in 0.1 M NaOH; electrolyte supernatant checks; recycled electrode analyses

Atmosphere: CO2 during e-CRR
Geometry: MOF/carbon/Nafion electrode
Context: stability of guest-loaded electrocatalyst under application conditions
Measurement source: 16 · Stability · Figures S22-S27

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
current density decrease after 4 h for CoPc@NU-1000-h	approximately 20% decrease	—	approximately	Text Approximate	16 · Stability · Figure S15
TEM-EDS Co atomic fraction after electrocatalysis for CoPc@NU-1000-l	Co 0.14%	—	—	Caption Exact Reported	18 · Stability · Figure S27
TEM-EDS Zr atomic fraction after electrocatalysis for CoPc@NU-1000-l	Zr 4.37%	—	—	Caption Exact Reported	18 · Stability · Figure S27
starting current density loss on reused films	approximately 25% low current density from original starting value	—	approximately	Text Approximate	16 · Stability · Figure S23
TBAPy linker leaching concentration	about 0.1 uM	—	about	Text Approximate	16 · Stability