Electrochemistry Application — Effective visible-light CO2 photoreduction over (metallo)porphyrin-based metal–organic frameworks to achieve useful hydrocarbons

6 measurement groups · 38 results

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

Mott-Schottky analysis

PCN-222(Fe)-modified GCE · Electrode

Mott-Schottky diagrams measured at different frequencies for PCN-222(Fe), PCN-222(Co), PCN-222(Ni), and PCN-222(Cu). SI electrode: polished glassy carbon electrode, MOF dispersed in water (1 mg/mL), catalyst suspension dropped twice onto GCE and dried at RT; BAS three-electrode cell with Pt counter, Ag/AgCl reference, 0.2 M Na2SO4 electrolyte deoxygenated with N2.

Temperature: room temperature
Atmosphere: N2-deoxygenated electrolyte
Geometry: modified glassy carbon electrode in three-electrode cell
Context: PCN-222(M)-modified glassy carbon electrodes prepared from pristine MOF powders
Measurement source: 5 · Bandgap level analysis · Figure 7b; Figures S8b-S10b

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
LUMO position of PCN-222(Co) versus Ag/AgCl	approximately -0.65 V vs Ag/AgCl	—	approximately	Text Approximate	5 · Bandgap level analysis · Figure S9b
LUMO position of PCN-222(Co) versus NHE	-0.45 V vs NHE	—	—	Text Approximate	5 · Bandgap level analysis · Figure S9b
LUMO position of PCN-222(Cu) versus Ag/AgCl	approximately -0.6 V vs Ag/AgCl	—	approximately	Text Approximate	5 · Bandgap level analysis · Figure S10b
LUMO position of PCN-222(Cu) versus NHE	-0.4 V vs NHE	—	—	Text Approximate	5 · Bandgap level analysis · Figure S10b
LUMO position of PCN-222(Fe) versus Ag/AgCl	approximately -0.65 V vs Ag/AgCl	—	approximately	Text Approximate	5 · Bandgap level analysis · Figure S8b
LUMO position of PCN-222(Fe) versus NHE	-0.45 V vs NHE	—	—	Text Approximate	5 · Bandgap level analysis · Figure S8b
LUMO position of PCN-222(Ni) versus Ag/AgClMarked as a best value within this paper	approximately -0.70 V vs Ag/AgCl	—	approximately	Text Approximate	5 · Bandgap level analysis · Figure 7b
LUMO position of PCN-222(Ni) versus NHEMarked as a best value within this paper	-0.50 V vs NHE	—	—	Text Approximate	5 · Bandgap level analysis · Figure 7b
Semiconductor type from Mott-Schottky slope	PCN-222(M) is an n-type semiconductor	—	—	Text Qualitative	5 · Bandgap level analysis · Figure 7b; Figures S8b-S10b

Visible-light photocatalytic CO2 reduction control experiments

FeTCPP, CoTCPP, NiTCPP, CuTCPP and H2TCPP ligand controls · Unknown

Figure 6 compares metalloporphyrinic MOFs with FeTCPP, CoTCPP, NiTCPP, CuTCPP, H2TCPP and negative controls.

Atmosphere: CO2 unless specified by control label
Geometry: batch photoreaction flask
Context: molecular ligand and reaction-condition controls
Measurement source: 5 · Photocatalytic reaction over PCN-222(M) · Figure 6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Ligand-control HCOO- yields after 10 h	FeTCPP, CoTCPP, NiTCPP, CuTCPP and H2TCPP all visually below about 6 umol at 10 h	—	upper-bound visual estimate	Visual Estimate Approximate	5 · Photocatalytic reaction over PCN-222(M) · Figure 6
Negative control HCOO- yields after 10 h	no TEOA, no CO2 and no PCN-222 controls remain near 0 umol	—	visual estimate from plotted traces	Visual Estimate Approximate	5 · Photocatalytic reaction over PCN-222(M) · Figure 6

Visible-light photocatalytic CO2 reduction with GC/GC-MS product quantification

PCN-222(Fe) · Powder

15 mg photocatalyst, 15 ml CH3CN, 1.5 ml TEOA; degassed by CO2 for 20 min, purged by CO2, visible-light irradiation using 500 W Xe lamp with UV/IR cut filter; products measured every 2 h by GC/MS. SI states GC used Agilent 6890 FID/HP-5 and GC-MS used Agilent 5973/HP-5 MS.

Atmosphere: CO2
Geometry: batch photoreaction flask
Context: pristine MOF photocatalysts and nonmetal control
Measurement source: 2-4 · Photocatalytic reaction; Photocatalytic reaction over PCN-222(M) · Figure 6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
CO and CH4 detection by GC/MS	CH4 and CO could not be detected; no CO is formed	—	—	Text Qualitative	4-7 · Photocatalytic reaction over PCN-222(M); Reaction mechanism · Figure S7
HCOO- formed over PCN-222(Co) by GC/MS after 10 h	47 umol in 10 h	—	—	Text Rounded Reported	4 · Photocatalytic reaction over PCN-222(M) · Figure 6b
HCOO- formed over PCN-222(Cu) by GC/MS after 10 h	50 umol in 10 h	—	—	Text Rounded Reported	4 · Photocatalytic reaction over PCN-222(M) · Figure 6d
HCOO- formed over PCN-222(Fe) by GC/MS after 10 h	52 umol in 10 h	—	—	Text Rounded Reported	4 · Photocatalytic reaction over PCN-222(M) · Figure 6a
HCOO- formed over PCN-222(Ni) by GC/MS after 10 hMarked as a best value within this paper	56 umol in 10 h	—	—	Text Rounded Reported	4 · Photocatalytic reaction over PCN-222(M) · Figure 6c
HCOO- formed over PCN-222(no metal) by GC/MS after 10 h	26 umol in 10 h	—	—	Text Rounded Reported	4 · Photocatalytic reaction over PCN-222(M) · Figure 6e

Ion mobility spectroscopy (IMS) product quantification

PCN-222(Fe) · Powder

Generated formate ion measured by IMS-400 (TOF Tech. Pars); drift time reported as 8.2 ms in SI Figure S6.

Atmosphere: CO2
Context: pristine metalloporphyrinic MOF photocatalysts
Measurement source: 4-5 · Photocatalytic reaction over PCN-222(M) · Figure S6

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
IMS drift time for generated formate ion	8.2 ms	—	—	Text Exact Reported	4 · Photocatalytic reaction over PCN-222(M) · Figure S6
HCOO- formed over PCN-222(Co) by IMS after 10 h	49 umol in 10 h	—	—	Text Rounded Reported	4-5 · Photocatalytic reaction over PCN-222(M) · Figure S7
HCOO- formed over PCN-222(Cu) by IMS after 10 h	53 umol in 10 h	—	—	Text Rounded Reported	4-5 · Photocatalytic reaction over PCN-222(M) · Figure S7
HCOO- formed over PCN-222(Fe) by IMS after 10 h	50 umol in 10 h	—	—	Text Rounded Reported	4-5 · Photocatalytic reaction over PCN-222(M) · Figure S7
HCOO- formed over PCN-222(Ni) by IMS after 10 hMarked as a best value within this paper	58 umol in 10 h	—	—	Text Rounded Reported	4-5 · Photocatalytic reaction over PCN-222(M) · Figure S7
Average formation of HCOO- for PCN-222(Co)	49 umol	—	—	Table Exact Reported	6 · Reaction mechanism and pathways of CO2 reduction · Table 1
Average formation of HCOO- for PCN-222(Cu)	53 umol	—	—	Table Exact Reported	6 · Reaction mechanism and pathways of CO2 reduction · Table 1
Average formation of HCOO- for PCN-222(Fe)	50 umol	—	—	Table Exact Reported	6 · Reaction mechanism and pathways of CO2 reduction · Table 1
Average formation of HCOO- for PCN-222(Ni)Marked as a best value within this paper	58 umol	—	—	Table Exact Reported	6 · Reaction mechanism and pathways of CO2 reduction · Table 1

Photocatalytic recycling experiment with post-reaction PXRD

X-ray diffraction and scattering

PCN-222(Fe) · Powder

Six 10 h photocatalytic reaction runs over PCN-222(Fe); product-yield bars and before/after PXRD are shown in rendered SI Figures S11-S12.

Atmosphere: CO2
Geometry: batch photoreaction flask
Context: recycled PCN-222(M) photocatalysts
Measurement source: 7 · Reaction mechanism and pathways of CO2 reduction · Figures S11-S12

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
PXRD structural integrity after photocatalytic reaction	before and after PXRD patterns retain the PCN-222(Fe) pattern qualitatively	—	—	Visual Estimate Qualitative	10 · S2.3. Characterization of catalyst · Figure S12
PCN-222(Fe) recycling run 1 product amountMarked as a best value within this paper	about 52 umol after 10 h in cycle 1	—	visual bar-height estimate	Figure Axis Approximate	10 · S2.3. Characterization of catalyst · Figure S11
PCN-222(Fe) recycling run 2 product amount	about 51 umol after 10 h in cycle 2	—	visual bar-height estimate	Figure Axis Approximate	10 · S2.3. Characterization of catalyst · Figure S11
PCN-222(Fe) recycling run 3 product amount	about 50 umol after 10 h in cycle 3	—	visual bar-height estimate	Figure Axis Approximate	10 · S2.3. Characterization of catalyst · Figure S11
PCN-222(Fe) recycling run 4 product amount	about 48 umol after 10 h in cycle 4	—	visual bar-height estimate	Figure Axis Approximate	10 · S2.3. Characterization of catalyst · Figure S11
PCN-222(Fe) recycling run 5 product amount	about 47 umol after 10 h in cycle 5	—	visual bar-height estimate	Figure Axis Approximate	10 · S2.3. Characterization of catalyst · Figure S11
PCN-222(Fe) recycling run 6 product amount	about 47 umol after 10 h in cycle 6	—	visual bar-height estimate	Figure Axis Approximate	10 · S2.3. Characterization of catalyst · Figure S11
Photocatalytic recycling stability over six runs	no noticeable change in product yields during six reaction runs	—	—	Text Qualitative	7 · Reaction mechanism and pathways of CO2 reduction · Figure S11

Tauc plot bandgap analysis from absorption spectra

UV-visible and optical absorption spectroscopy

PCN-222(Fe) · Powder

Bandgaps estimated from Tauc plots for PCN-222(Fe), PCN-222(Co), PCN-222(Ni), and PCN-222(Cu); UV-vis spectra obtained using Shimadzu UV-2600; supporting figures S8a, S9a, S10a and Figure 7a.

Context: pristine metalloporphyrinic MOF series
Measurement source: 5 · Bandgap level analysis · Figure 7a; Figures S8a-S10a

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Bandgap of PCN-222(Co)	1.9 eV	—	—	Text Rounded Reported	5 · Bandgap level analysis · Figure S9a
Bandgap of PCN-222(Cu)	1.97 eV	—	—	Text Rounded Reported	5 · Bandgap level analysis · Figure S10a
Bandgap of PCN-222(Fe)	1.8 eV	—	—	Text Rounded Reported	5 · Bandgap level analysis · Figure S8a
Bandgap of PCN-222(Ni)Marked as a best value within this paper	2 eV	—	—	Text Rounded Reported	5 · Bandgap level analysis · Figure 7a