Electrochemistry Application — Fibrous Pb(II)-Based Coordination Polymer Operable as a Photocatalyst and Electrocatalyst for High-Rate, Selective CO2-to-Formate Conversion

8 measurement groups · 75 results

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

Apparent quantum yield action spectrum

MW_60 fibrous KGF-9 powder · Powder

10 mg photocatalyst, 15 mL DMSO, 0.1 M BIH, CO2, 300 W Xe lamp, bandpass filters 350, 365, 400, 420, 460 and 500 nm, 0.4 mW cm-2.

Temperature: room temperature
Atmosphere: CO2
Geometry: irradiation area 1.8 cm x 1.8 cm
Context: Pristine MW_60 KGF-9 powder.
Measurement source: 9 · Experimental Section

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Formate production at 500 nm	lack of formate production at 500 nm	—	—	Text Qualitative	6 · 2.3 Improved Apparent Quantum Yield · Figure 4A
Maximum AQY at 400 nm over MW_60Marked as a best value within this paper	25%	—	—	Text Rounded Reported	6 · 2.3 Improved Apparent Quantum Yield · Figure 4A
AQY at 420 nm over MW_60	12.3%	—	—	Text Exact Reported	2 · Introduction
AQY at 400 nm for ordinary KGF-9	2.6%	—	—	Text Exact Reported	2 · Introduction

Light-intensity-dependent AQY and formate rate

MW_60 fibrous KGF-9 powder · Powder

400 nm Xe lamp bandpass; light intensity varied from 0.04 to 14 mW cm-2.

Temperature: room temperature
Atmosphere: CO2
Context: Pristine MW_60 KGF-9 powder.
Measurement source: 5 · 2.4 Light-Intensity-Dependent CO2 Reduction · Figure 4B,C

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
AQY range over 0.04-14 mW cm-2	ca. 20-25%	—	range 20-25%	Text Range	6 · 2.4 Light-Intensity-Dependent CO2 Reduction · Figure 4B
Light-intensity order for formate production rateMarked as a best value within this paper	I^1.0	—	—	Text Exact Reported	6 · 2.4 Light-Intensity-Dependent CO2 Reduction · Figure 4C
Estimated photogenerated charge-carrier recombination fraction	at least ca. 70%	—	lower bound	Text Approximate	6 · 2.4 Light-Intensity-Dependent CO2 Reduction

Linear sweep voltammetry and H-cell controlled-potential electrolysis

Voltammetry

KGF-9/Ketjen Black/Nafion electrode optimisation series · Electrode

0.5 M KHCO3 catholyte under Ar or CO2; H-type cell at -0.8 V vs RHE for 120 min; 25 uL 5 wt% Nafion; varied KB content.

Atmosphere: Ar and CO2
Geometry: carbon paper working electrode in H-cell
Context: Comparison of bare KGF-9, KB-containing KGF-9 and bare KB controls.
Measurement source: S-4 · Supporting Information · Table S5

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Bare KB electrode FE for H2	93.7%	—	—	Text Exact Reported	6 · 2.5 Electrocatalytic CO2-to-formate Conversion over KGF-9 · Figure 5B
Bare KGF-9 electrode FE for formate at -0.8 V	3.6%	—	—	Text Exact Reported	6 · 2.5 Electrocatalytic CO2-to-formate Conversion over KGF-9 · Figure 5B
Bare KGF-9 electrode FE for H2 at -0.8 V	98.4%	—	—	Text Exact Reported	6 · 2.5 Electrocatalytic CO2-to-formate Conversion over KGF-9 · Figure 5B
30 wt% KB KGF-9 electrode FE for CO at -0.8 V	0.8%	—	—	Text Exact Reported	6 · 2.5 Electrocatalytic CO2-to-formate Conversion over KGF-9 · Figure 5B
30 wt% KB KGF-9 electrode FE for formate at -0.8 VMarked as a best value within this paper	81.6%	—	—	Text Exact Reported	6 · 2.5 Electrocatalytic CO2-to-formate Conversion over KGF-9 · Figure 5B
30 wt% KB KGF-9 electrode FE for H2 at -0.8 V	19.2%	—	—	Text Exact Reported	6 · 2.5 Electrocatalytic CO2-to-formate Conversion over KGF-9 · Figure 5B
S5 CH4 product for 150 uL Nafion, 30 wt% KB	0.17 umol (0.56% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CO product for 150 uL Nafion, 30 wt% KB	0.5 umol (0.42% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 HCOO- product for 150 uL Nafion, 30 wt% KB	29 umol (23.7% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 H2 product for 150 uL Nafion, 30 wt% KB	93 umol (75.6% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CH4 product for 15 uL Nafion, 30 wt% KB	n.d. (0)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CO product for 15 uL Nafion, 30 wt% KB	3.5 umol (3.9% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 HCOO- product for 15 uL Nafion, 30 wt% KB	53 umol (60% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 H2 product for 15 uL Nafion, 30 wt% KB	18 umol (20.4% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CH4 product for 25 uL Nafion, 0 wt% KB	0.03 umol (0.23% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CO product for 25 uL Nafion, 0 wt% KB	n.d. (0)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 HCOO- product for 25 uL Nafion, 0 wt% KB	2 umol (3.6% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 H2 product for 25 uL Nafion, 0 wt% KB	52 umol (98.4% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CH4 product for 25 uL Nafion, 100 wt% KB	n.d. (0)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CO product for 25 uL Nafion, 100 wt% KB	n.d. (0)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 HCOO- product for 25 uL Nafion, 100 wt% KB	n.d. (0)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 H2 product for 25 uL Nafion, 100 wt% KB	175 umol (93.7% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CH4 product for 25 uL Nafion, 10 wt% KB	0.08 umol (1.6% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CO product for 25 uL Nafion, 10 wt% KB	0.1 umol (0.5% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 HCOO- product for 25 uL Nafion, 10 wt% KB	9 umol (33.7% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 H2 product for 25 uL Nafion, 10 wt% KB	13 umol (47.4% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CH4 product for 25 uL Nafion, 20 wt% KB	0.06 umol (0.47% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CO product for 25 uL Nafion, 20 wt% KB	2 umol (2.1% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 HCOO- product for 25 uL Nafion, 20 wt% KB	52 umol (68.4% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 H2 product for 25 uL Nafion, 20 wt% KB	19 umol (25.4% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CH4 product for 25 uL Nafion, 30 wt% KB	0.046 umol (0.23% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CO product for 25 uL Nafion, 30 wt% KB	0.6 umol (0.8% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 HCOO- product for 25 uL Nafion, 30 wt% KBMarked as a best value within this paper	64 umol (81.6% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 H2 product for 25 uL Nafion, 30 wt% KB	15 umol (19.2% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CH4 product for 25 uL Nafion, 40 wt% KB	0.037 umol (0.19% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CO product for 25 uL Nafion, 40 wt% KB	2 umol (2.7% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 HCOO- product for 25 uL Nafion, 40 wt% KB	51 umol (65.7% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 H2 product for 25 uL Nafion, 40 wt% KB	22 umol (27.6% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CH4 product for 50 uL Nafion, 30 wt% KB	0.055 umol (0.26% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 CO product for 50 uL Nafion, 30 wt% KB	2 umol (2.3% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 HCOO- product for 50 uL Nafion, 30 wt% KB	59 umol (68.3% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5
S5 H2 product for 50 uL Nafion, 30 wt% KB	33 umol (38.2% FE)	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S5

H-cell CO2 reduction over optimised KGF-9 electrode at varied potential

KGF-9 electrode with 30 wt% KB and 25 uL 5 wt% Nafion · Electrode

KGF-9 (MW_60) working electrodes with 30 wt% KB and 25 uL 5 wt% Nafion; catholyte 0.5 M KHCO3 aq. pH 6.8; anolyte 0.5 M KOH aq.; Pt foil counter; Ag/AgCl reference; 120 min; no iR compensation.

Atmosphere: CO2 or Ar
Geometry: H-type electrochemical cell
Context: Optimised composite electrode derived from pristine KGF-9.
Measurement source: 7 · Table 1 · Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Electrolysis TON for formate at -1.0 V	36 within 300 min	—	—	Text Exact Reported	6 · 2.5 Electrocatalytic CO2-to-formate Conversion over KGF-9
Absolute partial current density for formate at -1.0 VMarked as a best value within this paper	4.5 mA cm-2	—	—	Text Exact Reported	6 · 2.5 Electrocatalytic CO2-to-formate Conversion over KGF-9 · Figure 6, Table 1
KGF-9/30 wt% KB comparison-table FEformateMarked as a best value within this paper	92.7%	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S6
KGF-9/30 wt% KB comparison-table jformate	4.5 mA cm-2	—	—	SI Table Exact Reported	S-4 · Supporting Information · Table S6
H2 under Ar at -1.0 V	958 umol (87.0% FE); formate n.d.	87 % FE H2	—	Table Exact Reported	7 · Table 1 · Table 1
Formate at -0.6 V vs RHE under CO2	n.d. (0%)	0 % FE	—	Table Exact Reported	7 · Table 1 · Table 1
Formate at -0.7 V vs RHE under CO2	7 umol (11.9% FE)	11.9 % FE	—	Table Exact Reported	7 · Table 1 · Table 1
Formate at -0.8 V vs RHE under CO2	64 umol (81.6% FE)	81.6 % FE	—	Table Exact Reported	7 · Table 1 · Table 1
Formate at -0.9 V vs RHE under CO2	163 umol (79.2% FE)	79.2 % FE	—	Table Exact Reported	7 · Table 1 · Table 1
Formate at -1.0 V vs RHE under CO2Marked as a best value within this paper	254 umol (92.7% FE)	92.7 % FE	—	Table Exact Reported	7 · Table 1 · Table 1

High-rate constant-current eCO2RR in three-compartment cell

Galvanostatic cycling

KGF-9/Ketjen Black gas diffusion electrode · Electrode

Catholyte and anolyte 1 M KHCO3 aq. pH 6.8; CO2 gas 99.99% to gas chamber at 10 sccm; total current densities 200 and 300 mA cm-2; 30 min; no iR compensation.

Atmosphere: CO2
Geometry: gas diffusion electrode in three-compartment electrochemical cell
Context: Composite GDE using MW_60 KGF-9 pre-catalyst and conductive KB.
Measurement source: 8 · 2.7 High-Rate CO2-to-Formate Conversion · Figure 7

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
High-rate FEformate at Jtot 200 mA cm-2Marked as a best value within this paper	95.4% at 200 mA cm-2	—	—	Text Exact Reported	8 · 3 Conclusion · Figure 7A
High-rate FEformate at Jtot 300 mA cm-2	93.7% at 300 mA cm-2	—	—	Text Exact Reported	8 · 3 Conclusion · Figure 7A
High-rate partial current density for formate at Jtot 200 mA cm-2	191 mA cm-2	95.3 % FEformate	—	Text Exact Reported	8 · 2.7 High-Rate CO2-to-Formate Conversion · Figure 7A
High-rate partial current density for formate at Jtot 300 mA cm-2Marked as a best value within this paper	281 mA cm-2	93.7 % FEformate	—	Text Exact Reported	8 · 2.7 High-Rate CO2-to-Formate Conversion · Figure 7A
Total current density condition, high-rate lower setting	200 mA cm-2	—	—	Text Exact Reported	8 · 2.7 High-Rate CO2-to-Formate Conversion · Figure 7A
Total current density condition, high-rate upper settingMarked as a best value within this paper	300 mA cm-2	—	—	Text Exact Reported	8 · 2.7 High-Rate CO2-to-Formate Conversion · Figure 7A

H-cell CO2 reduction for Pb carbonate controls

bare PbCO3 working electrode · Electrode

Table 1 control measurements at -0.9 V vs RHE under CO2 using PbCO3 and Pb3(CO3)2(OH)2 working electrodes.

Atmosphere: CO2
Geometry: H-type electrochemical cell
Context: Non-MOF control electrocatalysts.
Measurement source: 7 · Table 1 · Table 1

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Pb3(CO3)2(OH)2 control formate at -0.9 V	130 umol (56.8% FE)	56.8 % FE	—	Table Exact Reported	7 · Table 1 · Table 1
PbCO3 control formate at -0.9 V	108 umol (51.7% FE)	51.7 % FE	—	Table Exact Reported	7 · Table 1 · Table 1

Photocatalytic CO2 reduction under visible LED light

MW_x KGF-9/KGF-17 comparison powder series · Powder

4 mg photocatalyst, 4 mL DMSO, 0.1 M BIH, CO2 bubbling 30 min, LED 370 <= lambda <= 500 nm, 10 mW, 300 min.

Temperature: room temperature
Atmosphere: CO2
Geometry: merry-go-round photoreactor
Context: Pristine and mixed CP powder photocatalysis.
Measurement source: 9 · Experimental Section

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Formate production by MW_60 after 300 minMarked as a best value within this paper	209 +/- 25 umol	—	+/- 25 umol	Text Exact Reported	4 · 2.2 Photocatalytic CO2 Reduction Activity · Figure 2A
Photocatalytic selectivity to formateMarked as a best value within this paper	>99%	—	lower bound	Text Approximate	3 · 2.2 Photocatalytic CO2 Reduction Activity · Figure 2A

Photocatalytic CO2 reduction time course and isotope labelling

MW_60 fibrous KGF-9 powder · Powder

MW_60 under LED visible light with BIH in DMSO; 13CO2 tracer experiment analysed by 1H NMR.

Temperature: room temperature
Atmosphere: CO2 or 13CO2
Geometry: sealed reaction cell
Context: Pristine MW_60 KGF-9 powder.
Measurement source: 5 · 2.2 Photocatalytic CO2 Reduction Activity · Figure 3

Property	Reported value	Normalised value	Uncertainty	Origin and quality	Source
Formate production at 10% CO2	67 umol at 10% CO2	—	—	Text Rounded Reported	5 · 2.2 Photocatalytic CO2 Reduction Activity · Figure S10
Saturated formate production after 600 min	ca. 250 umol	—	—	Text Approximate	4 · 2.2 Photocatalytic CO2 Reduction Activity · Figure S9
Formate after 60 min irradiation	22 umol	—	—	Text Rounded Reported	4 · 2.2 Photocatalytic CO2 Reduction Activity · Figure 3A
1H-13C coupled formate signals from 13CO2	8.75 and 8.32 ppm, J13CH = 170 Hz	—	—	Text Exact Reported	5 · 2.2 Photocatalytic CO2 Reduction Activity · Figure 3B
1H NMR formate signal from non-labelled CO2	8.48 ppm	—	—	Text Exact Reported	5 · 2.2 Photocatalytic CO2 Reduction Activity · Figure 3B
Photocatalytic TON for formate over MW_60	18	—	—	Text Exact Reported	4 · 2.2 Photocatalytic CO2 Reduction Activity