1

Supplementary Information for Precious metal recovery from electronic waste by a porous porphyrin polymer Yeongran Hong, Damien Thirion, Saravanan Subramanian, Mi Yoo, Hyuk Choi, Hyun You Kim, J. Fraser Stoddart, and Cafer T. Yavuz J. Fraser Stoddart and Cafer T. Yavuz Email: stoddart@northwestern.edu, yavuz@kaist.ac.kr This PDF file includes:

Supplementary text Schemes S1 and S2 Figures S1 to S14 Tables S1 to S6 SI References

www.pnas.org/cgi/doi/10.1073/pnas.2000606117

2

Supplementary Information Text Materials. Copper (II) nitrate trihydrate (puriss. p.a., 99-104 %), gold (III) chloride trihydrate (≥ 99.9 %), nickel (II) nitrate hexahydrate (99.999 %), pyrrole (98 %), and p-phenylenediamine (≥ 99.0 %) were purchased from Sigma-Aldrich, USA. 4-Nitrobenzaldehyde (99 %) and potassium hydroxide (99.98 %, pellets, KOH) were obtained from Alfa-Aesar, USA. Acetic anhydride (99.0 %), aniline (99.0 %), propionic acid (99.0 %), and silver nitrate (99.8 %) were purchased from SAMCHUN, South Korea. N,N-Dimethylformamide (99.5 %, DMF) and pyridine (99.5 %) were from DAEJUNG, South Korea. Potassium tetrachloroplatinate (II) (46-47 % Pt) was purchased from Acros Organics, Belgium. Palladium (II) nitrate hydrate (99 %) was from KOJIMA, Japan. DMF was dried using the glass contour ultimate solvent purification system (Nikko Hansen, Japan). Pyrrole was distilled before use and consumed within a week. KOH was used as a drying agent for the pyrrole distillation. Other materials were used without further purification. For all metal adsorption and desorption experiments, deionized water (DIW) obtained from Mili-Q (18.2 MQ·cm at 25 oC) system was used.

Methods Synthesis of COP-180 and derivatives.

The monomer, 5,10,15,20-Tetrakis(4-nitrophenyl)-21H,23H-porphyrin (TNPPH2), was synthesized according to the literature (1, 2) with slight modification: Briefly, 4-nitrobenzaldehyde and pyrrole were cyclized in propionic acid in the presence of acetic anhydride. The precipitate was filtered and washed with water and methanol and dried under vacuum. The dark powder was dissolved in pyridine and refluxed for 1 h. The final product was collected by vacuum filtration, washed with acetone, and further purified by Soxhlet extraction with acetone. Yield: 16 %. 1H NMR (CDCl3, 300 MHz, ppm): δ 8.40 (d, 8H, J=8.3 Hz), 8.67 (d, 8H, J=8.4 Hz), 8.82 (s, 8H). Anal. Calcd for C44H26N8O8: C, 66.50; H, 3.30; N, 14.10; O, 16.10 %. Found: C, 66.53; H, 3.33; N, 14.48; O, 16.02 %.

Synthesis of COP-180 was conducted by a modified procedure from the literature (3-5): TNPPH2 (1 g), p-phenylenediamine (275 mg), and KOH (710 mg) were added to dry DMF (200 mL). The mixture was stirred for 1 h under nitrogen purge. The mixture was heated to 150 oC and refluxed for 24 h under nitrogen atmosphere. After cooling to room temperature, the reaction mixture was poured into 1 L of DIW and stirred for 1 h. The precipitate was collected by filtration and purified by Soxhlet extraction method with water and acetone for a day each. The product was dried at 150 oC for a day in vacuum oven. Yield: 75 %. Synthesis of model compound (TNPPH2A). The model compound was prepared by following the same synthetic method as COP-180. TNPPH2 (200 mg) and KOH (142 mg) were added to dry DMF (40 mL). Instead of p-phenylenediamine, excess amounts of aniline (5 mL) was used.

3

Synthesis of azo-linked porphyrin polymer (COP-180Azo). The same synthetic procedure was employed to prepare azo-linked porphyrin polymer. The polymer was synthesized by reacting TNPPH2 (200 mg) and 2,3,5,6-Tetramethyl-p-phenylenediamine (84 mg), instead of p-phenylenediamine, in 40 mL of dry DMF in the presence of KOH (142 mg). Characterizations. Fourier-transform infrared spectroscopy (FT-IR) spectra were collected using a JASCO FT-IR spectrometer 4100 on KBr pellets. Liquid 1H nuclear magnetic resonance (NMR) was performed by a Bruker NMR spectrometer at 300 MHz. Solid-state 13C cross-polarization magic-angle spinning (CP/MAS) NMR spectroscopy was conducted by a Varian Unity INOVA 500 MHz spectrometer using a 3.2 mm chemagnetics probe-head. The 13C NMR spectra were taken at a spinning speed of 15 kHz, contact time of 1,900 μs, and delay time of 5 s with TMS as standard. The number of scans for each 13C NMR spectrum was 20,000. Elemental analysis for C, H, N, and O was carried out using a FLASH 2000 series of Thermo Scientific. High resolution mass spectrum was acquired by a micrOTOF-Q II of Bruker Daltonik. For the porosity of samples, nitrogen adsorption-desorption isotherms were measured using a Micromeritics Triflex accelerated surface area and porosimetry analyser at 77 K after the samples had been degassed at 150 oC overnight under vacuum. The specific surface areas of the samples were determined according to the Brunauer-Emmett-Teller (BET) model and the pore size distribution was calculated by the Non-Local Density Functional Theory (NLDFT) method. Powder X-ray diffraction (PXRD) patterns of samples were measured over the 2θ range of 3-90o on a Rigaku D/MAX-2500 (18 kW) Multi-purpose High power X-ray diffractometer. X-ray photoelectron spectroscopy (XPS) was conducted on a K-alpha model of Thermo VG Scientific equipped with a microfocused monochromator X-Ray source with the energy resolution of 0.5 eV full-width at half-maximum under ultrahigh vacuum condition of 10-9 Torr. Field emission transmission electron microscopy (TEM) images were recorded on a Talos F200X model of FEI. Single metals were observed by Titan Double Cs corrected TEM of FEI (Titan cubed G2 60-300). The ICP-MS instrument of Agilent 7700x model was used for metal analysis and multi-element standard solutions from Agilent technologies (Agilent part no. 8500-6940, 8500-6942, 8500-6944, 8500-6948) were used for calibration and metal selectivity tests. Thermogravimetric analysis (TGA) was carried out with a differential thermal gravimetry (DTG)-60A of Shimadzu at a heating rate of 10 oC min–1 up to 800 oC under air and nitrogen atmosphere, respectively. The ultraviolet–visible (UV/vis) absorbance spectra of samples were obtained by JASCO V-570 spectrometer in solid state.

Metal selectivity tests. The multi-element calibration standard solution at 10 ppm for each metal was diluted to 100 ppb of 60 mL with DI water. The dilute solution was divided to 10 mL of three samples for the control group and 10 mL of the other three samples for the experimental group. To the three samples of the experimental group, COP-180 (10 mg each) was added. All the samples were tumbled at 8 rpm for 24 h and filtered using syringe filters (ADVANTEC, pore size = 0.50 μm). The concentration of metals in the samples were analysed by ICP-MS. The adsorption amounts of each metal were calculated by the comparison of concentrations between the control and experimental group:

Uptake(%) =𝐶𝑐 − 𝐶𝑒𝐶𝑐 𝑋100(%)

where Cc and Ce are the average concentrations of the control group and the experimental group, respectively.

This method was repeated for four different standard solutions and the mixed solution of standards 1 and 2 in order to confirm the high selectivity towards precious metals of COP-180 compared to other common metals. In the case of the mixed solution, the uptake of silver ions was excluded due to the

4

possibility of precipitate formation with hydrochloric acid that is included in the standard solution 2 as a matrix agent.

Single batch adsorption. Potassium tetrachloroplatinate (II) (320 mg), gold (III) chloride trihydrate (300 mg), palladium (II) nitrate hydrate (326 mg), silver nitrate (236 mg), copper (II) nitrate trihydrate (570 mg), and nickel (II) nitrate hexahydrate (743 mg) were dissolved in DIW (50 mL), individually. All metal solutions were filtered once to remove the undissolved salts. To each solution, COP-180 (500 mg) was added. All suspensions were shaken at 8 rpm for 48 h. After 48 h, the polymer was separated by filtration with filter paper (Whatman, pore size = 11 μm) and washed thoroughly with DIW. The metal loaded polymers were dried in vacuum oven at 100 oC.

Gold and platinum adsorption isotherms. The gold solutions at 20, 100, 500, 1,000, 3,000 and 5,000 ppm were prepared by diluting the stock solution of gold (III) chloride trihydrate. One of the 10 mL solutions and two of the 10 mL solutions at each concentration were used as a control and experimental group, respectively. COP-180 (10 mg each) was added to the experimental group. After shaking the mixtures for 60 h at 8 rpm, the polymer was filtered off and the gold concentrations were measured by ICP-MS. The captured metal amounts were calculated by concentration comparison between control and experimental group of the solutions. The same experimental procedure was repeated to measure the platinum adsorption capacity of COP-180 using 10, 20, 200, 500, 800, and 1,000 ppm of platinum solutions prepared from the potassium tetrachloroplatinate (II) stock solution.

In order to confirm the effects of the light on gold adsorption, the same experiment was conducted under light irradiation (halogen lamp, 42 W, 630 lm) using 20, 100, 500, 1,000, 3,000 and 5,000 ppm of gold solutions. Half of the solutions at each concentration were prepared in transparent vials and the other half was in brown vials which were covered with aluminum foil to protect the solutions from light. All vials were in the same oil bath under the lamp to maintain the same temperature of 34 oC. The solutions were stirred and filtered after 60 h. The gold adsorption amount by COP-180 in dark condition at room temperature was also measured using 20, 100, 500, 1,000, 3,000 and 5,000 ppm of gold solutions. The shaking and filtration processes were carried out in a dark room.

The gold and platinum adsorption isotherms were fitted by Langmuir adsorption model. The equation of Langmuir model is represented as follows:

𝑄! =𝑄" ∙ 𝐾# ∙ 𝐶!1 + 𝐾# ∙ 𝐶!

(Linearizedform:𝐶!𝑄!

=1𝑄"

𝐶! +1

𝐾# ∙ 𝑄")

where Qe (gAu/ gAds) is the quantity of adsorbed metal ions in a gram of adsorbent at equilibrium, Ce (mg L–1) is the equilibrium concentration, Qm (gAu/ gAds) is the maximum uptake amounts of metal ions in a gram of adsorbent, and KL is the Langmuir constant. The pH of solutions was measured and displayed below.

Gold solutions Platinum solutions Concentration

(mg/L) pH Concentration

(mg/L) pH

20 3.95 10 6.60 100 3.16 20 6.64 500 2.66 200 6.24 1000 2.46 500 6.34 3000 2.14 800 6.55 5000 1.97 1000 6.29

5

pH Effects on metal adsorption. The changes in metal adsorption behavior of COP-180 depending on the pH of solution were investigated as follows. The stock solutions of gold and platinum were diluted to 100 ppb each, and at the same time with the dilution, the pH of the solutions was adjusted by adding dropwise 0.1 M of HCl and 0.1 M of NaOH solutions. Three of the 10 mL control samples and three of the 10 mL of experimental samples were prepared for each adsorption time. COP-180 (10 mg each) was added to the experimental samples. All samples were tumbled at 8 rpm and after 30 min, 1 h, 3 h, 6 h, 12 h, and 24 h, COP-180 was filtered using the syringe filter units. The gold and platinum concentrations were analysed by ICP-MS.

Metal desorption and reusability. 5 %, 10 % and 30 % of HNO3 solutions and a mixed solution of 18 % HNO3 and 2 % HCl were prepared. The metal loaded COP-180s prepared in the single batch adsorption experiment were used for the metal desorption tests. 3 mg of each metal loaded polymer was placed in a glass vial and 10 mL of acid solution was added. The mixtures were placed in a sand bath at 60 oC and kept for 6, 12, 24, 36, and 48 h while stirring. After each time, the polymer was removed by filtration and the concentrations of desorbed metals in filtrate were measured using ICP-MS. The desorption efficiency was calculated based on the metal loading amounts from ICP-MS data in the single batch adsorption test.

Precious metal capture from actual e-waste. The printed circuit boards (PCBs) were obtained from the local junk shop. The metals in PCBs were leached by following the modified method described in the literature (6). First, the PCBs were soaked in 10 M of NaOH solution for a day to remove the epoxy on the surface. The PCBs were taken out and washed with tap water. Then, the PCBs were soaked in 4 L of 1 M of HCl and HNO3 solution. The temperature of the solution was raised to 40 oC and held for two days. The PCBs were taken out and the acidic solution was filtered to remove any undissolved parts. KOH was added to the solution to reach a positive pH value and DIW was added to make a 5 L of the final solution. 1 g of COP-180 was added to the solution and the mixture was stirred for two days. After filtering, COP-180 was washed thoroughly with deionized water. The loaded metals on COP-180 were analysed by ICP-MS and their amounts were compared with the metal concentrations of the solution before COP-180 injection.

Theoretical calculations. We performed spin-polarized DFT calculations with the Vienna ab-initio simulation package (VASP) (7) with the HSE06 (8) hybrid functional. Electron wave functions were expanded with plane waves up to an energy cutoff of 400 eV. The interactions between the ionic cores of atoms and valance electrons were described with the projected augmented wave method (9). A 40Å×40Å×23Å supercell was applied for all calculations. A COP-180 unit was located in the center of the supercell. This model provides at least 10 Å of spacing between adjacent repeating COP-180 units. The van der Waals-corrected DFT-D3 method (10) was applied for all calculations. The Brillouin zone was sampled at the G-point. The convergence criteria for the electronic structure and the atomic geometry were set to 10-4 eV and 0.05 eV/Å, respectively. We used a Gaussian smearing function with a finite temperature width of 0.2 eV to improve the convergence of the states near the Fermi level.

A single COP-180 unit was used to calculate the binding energy of Au and Pt on COP-180. Au and Pt atoms were sequentially adsorbed at the central N ions of porphyrin to calculate the sequential binding energy, Ebind, of Au and Pt. We found that metallic ions do not interact with the phenazine linker of COP-180. The most stable binding site of metallic ions was found and reported in Fig. 3. The Ebind of a metal ion on a COP-180 was calculated referenced to the integrated total energy of a COP-180 unit, two metal chloride ions, and n/2·H2 molecules. The number of H atoms, n/2, was balanced to the residual number of Cl ions to be removed from metal chlorides upon adsorption to a COP-180. The first Ebind was calculated by removing two Cl- ions of AuCl3 and PtCl2 as gas phase HCl molecules with the protons of the NH radicals of porphyrin. The remaining Cl ion of the AuCl was artificially removed by forming a HCl molecule with additionally supplied H atom.

6

SI Schemes, Figures and Tables

a

b

Scheme S1. Probable synthetic mechanisms of (a) phenazine and (b) azobenzene formation from the reaction of nitro and amino groups, respectively. The reaction mechanisms were reproduced from the

literature (11, 12).

7

a

b

Scheme S2. Syntheses of (a) TNPPH2A and (b) COP-180Azo.

8

Fig. S1. Structural characterisation of COP-180 and comparison with TNPPH2A and COP-180Azo. (a) Pore size distribution of COP-180. (b) FT-IR spectra of TNPPH2, COP-180, TNPPH2A, and COP-180Azo. (c) Nitrogen adsorption-desorption isotherms of COP-180 and COP-180Azo at 77 K. (d) 13C CP/MAS solid-state NMR spectra of COP-180 and COP-180Azo and assigned peaks in the suggested structures and table.

0 20 40 60 80 1000.20

0.25

0.30

0.35

0.40

0.45

0.50

0.55

Pore width (nm)

Cum

ulat

ive

pore

vol

ume

(cm

3 /g)

0.0000

0.0005

0.0010

0.0015

0.0020

dV/d

W P

ore

volu

me

(cm

3 /g×n

m)

250 200 150 100 50 0

Chemical shift (p.p.m.)

COP-180Azo

30

113131

142149

163

115128

133

141

156161

COP-180

250 200 150 100 50 0

a d

c COP-180 (SA: 704 m2/g)COP-180Azo (SA: 44 m2/g)

0.0 0.2 0.4 0.6 0.8 1.0

050

100150200250300350400

Qua

ntity

ads

orbe

d (c

m3 /g

)

Relative pressure (p/po)

b

9

Fig. S2. XRD patterns of COP-180-Ag, COP-180-Pd, COP-180-Cu, COP-180-Ni, and COP-180.

Fig. S3. Thermogravimetric analysis of COP-180 and metal-loaded COP-180s (a) in air and (b) in nitrogen

atmosphere.

10 20 30 40 50 60 70 80 90

2 Theta (degree)

Inte

nsity

(a.u

.)

COP-180

(111)

(200)(220) (311) (222)

COP-180-Ag

COP-180-Pd

COP-180-Cu

COP-180-Ni

20 30

a b

10

Fig. S4. XPS spectra of COP-180 and metal-loaded COP-180s. (a) N (1s) and (b) Cu (2p), Pd (3d), and

Ag (3d) on COP-180.

Fig. S5. Stability of COP-180 after acid treatment. (a) Nitrogen adsorption-desorption isotherms and (b)

FT-IR spectrum of COP-180 after acid treatment.

a b

a b

11

Fig. S6. Nitrogen adsorption-desorption isotherms and BET surface areas of metal loaded COP-180s

measured at 77 K. (a) COP-180-Ni, COP-180-Ag and COP-180-Au, and (b) COP-180-Pd, COP-180-Cu

and COP-180-Pt. The nitrogen adsorption and desorption of COP-180 at 77 K was inserted in both graphs for comparison.

Fig. S7. UV-Vis absorption spectra of TNPPH2, COP-180 and metal loaded COP-180s.

a b

12

Fig. S8. Gold adsorption isotherms of COP-180 with linearized Langmuir fits. (a) at ambient light and room

temperature, (b) under light irradiation at 34 oC (with the natural temperature increase due to the light

irradiation, no external heating used), (c) in dark at room temperature and (d) in dark at 34 oC.

a b

c d

0 1000 2000 3000 40000.0

0.4

0.8

1.2

1.6

2.0

0 1000 2000 3000

0

500

1000

1500C

e / Q

e

Ce (mg L-1)

y = 0.61843x + 7.66971R2 = 0.9996

Au g

/ ads

orbe

nt g

Equilibrium concentration (p.p.m.)

0 1000 2000 3000 40000.0

0.4

0.8

1.2

1.6

2.0

0 1000 2000 3000 4000

0

500

1000

1500

2000

2500

Ce

/ Qe

Ce (mg L-1)

y = 0.52866x + 1.78003R2 = 0.99994

Au g

/ ads

orbe

nt g

Equilibrium concentration (p.p.m.)

0 1000 2000 3000 40000.0

0.4

0.8

1.2

1.6

2.0

0 1000 2000 3000

0

500

1000

1500

2000

Ce

/ Qe

Ce (mg L-1)

y = 0.65135x + 9.74871R2 = 0.99942

Au g

/ ads

orbe

nt g

Equilibrium concentration (p.p.m.)

0 1000 2000 3000 40000.0

0.4

0.8

1.2

1.6

2.0

0 1000 2000 3000 4000

0

500

1000

1500

2000

2500

3000

Ce

/ Qe

Ce (mg L-1)

y = 0.637296x + 0.51706R2 = 1

Au g

/ ads

orbe

nt g

Equilibrium concentration (p.p.m.)

13

Fig. S9. Metal selectivity test results using ICP-MS standard solutions*. (a) Standard solution-1, (b) -2, (c)

mixed solution of 1 and 2, (d) -3, and (e) -4, from top to bottom.

a

b

c

d

e

14

*The negative adsorption efficiencies of some of the metals above are considered to be due to the contamination of the samples from the commonly present elements in water and on the experimental tools, and also from the standard deviation of the measured values. Several elements with large negative values such as sodium, magnesium, potassium, calcium, zinc, and silicon were excluded for the clarity of the figure. Silver was excluded in the third table (c) in consideration of possible formation of silver chloride with HCl which is the matrix component of standard solution-1.

Fig. S10. FT-IR spectra of COP-180 and metal-loaded COP-180s.

15

a

b c

Fig. S11. STEM images of (a) gold, (b) platinum adsorbed COP-180s and (c) bare COP-180.

16

Fig. S12. Electron microscopy. (a) TEM images of metal loaded COP-180s. STEM and elemental

mapping images of (b) COP-180-Ag, (c) COP-180-Pd, and (d) COP-180-Cu.

a

b

c

d

17

Fig. S13. EPR spectra of the spent COP-180 in gold and platinum adsorption at 77 K.

Fig. S14. Regeneration test results of (a) COP-180-Pt, (b) COP-180-Pd, and (c) COP-180-Ag.

Name g-factor COP-180 2.0008 COP-180-Au 2.0012 COP-180-Pt 2.0017

b

c

a

2.04 2.02 2.00 1.98 1.96

-5

0

5

Inte

nsity

g factor

COP180 COP180-Au COP180-Pt

18

Table S1. Elemental analyses of TNPPH2, COP-180, TNPPH2A, and COP-180Azo.

Table S2. Elemental analyses of metalated COP-180s. The metal contents were measured by ICP-MS.

Element C N H O

TNPPH2 Calculated (%) 66.50 14.10 3.30 16.10

Found (%) 66.53 14.48 3.33 16.02

COP-180

Calculated (%) - Phenazine 77.59 19.39 3.02 0

Calculated (%) - Azo 76.87 19.21 3.92 0

Found (%) 73.80 14.72 3.90 4.70

TNPPH2A

Calculated (%) - Phenazine 79.83 16.43 3.74 0

Calculated (%) - Azo 79.20 16.30 4.50 0

Found (%) 73.92 14.93 4.24 2.86

COP-180Azo Calculated (%) 77.87 17.02 5.11 0

Found (%) 71.85 13.70 4.45 7.74

C N H O Metal

COP-180Au 54.18 10.91 2.77 3.12 Au 21.60

COP-180Pt 58.22 14.48 3.68 3.71 Pt 13.29

K 0.53

COP-180Ag 66.94 13.70 3.53 3.65 Ag 8.45

COP-180Pd 72.60 14.82 3.85 3.70 Pd 2.15

COP-180Cu 72.33 14.86 3.78 2.80 Cu 4.12

COP-180Ni 75.00 15.62 4.09 3.10 Ni 0.04

19

Table S3. (a) Metal contents from the printed circuit boards used in this study.

(b) The sizes and weights of the printed circuit boards used in the study.

No. Metal Metal content (mg/g)

No. Metal Metal content (mg/g)

1 Na 91.86515 15 Mo 0.021335

2 Cu 81.03541 16 Mg 0.019186

3 Sn 31.89889 17 Ag 0.011448

4 Zn 18.56148 18 Be 0.008725

5 Fe 9.031367 19 Co 0.007935

6 Pb 2.863421 20 Au 0.006996

7 Al 1.948036 21 Cr 0.006032

8 Ni 0.864876 22 Sr 0.005328

9 Ba 0.688929 23 Y 0.004676

10 Ti 0.230107 24 As 0.004548

11 Ga 0.133902 25 Zr 0.004527

12 Te 0.036257 26 Sb 0.003991

13 W 0.026307 27 Rb 0.00268

14 Mn 0.02547

No. Size (width x length in cm) Weight (g)

1 9.4 x 16.7 104.72

2 9.4 x 16.7 111.50

3 8.6 x 20.0 74.48

4 12.2 x 19.0 162.04

5 10.4 x 14.3 80.48

6 7.2 x 12.4 56.02

7 10.0 x 9.5 56.98

20

Table S4. Information on the ICP-MS standard solutions obtained from Agilent.

Table S5. Elemental composition of the gold ingot obtained from electronic waste. The organic contents

were measured by elemental analysis and the gold percentage was measured by ICP-MS.

C H N S O Au % 0.125 0 0.240 0 0.196 99.62

Table S6. Rough cost estimate for COP-180 synthesis. Prices are based on quotes. Actual costs will

vary. Labor and utilities are not included.

1Vendors: aSamchun(Leapchem), bSamchun, cSamchun(Dayang), dSigma-Aldrich

No. Agilent Part No. Matrix Labeled Conc. (mg L–1)

Metals

1 8500-6948 10 % HCl, 1 % HNO3 10.0 Ru, Rh, Pd, Sn, Sb, Te, Hf, Ir, Pt, Au

2 8500-6940 5 % HNO3 10.0 Li, Be, Na, Mg, Al, K, Ca, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, As, Se, Rb, Sr, Ag, Cd, Cs, Ba, Tl, Pb, U

3 8500-6942 0.2 % HF, Tr. HNO3 10.0 B, Si, P, S, Ti, Ge, Zr, Nb, Mo, Ta, W, Re

4 8500-6944 5 % HNO3 10.0 Sc, Y, La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu, Th

Exp. Chemical1 Price ($) Amount Cost in a scale up run ($)

Monomer (TNPPH2) Synthesis

4-Nitrobenzaldehydea Acetic anhydrideb Propionic acidc Pyrrolec Pyridineb

$2,400/25kg $75/20kg $2,400/200kg $2,600/25kg $275/18L

1.1kg 1.2kg 30kg 500g 8L

$105 $4.5 $360 $52 $123

Polymer (COP-180) Synthesis

TNPPH2 (monomer) p-Phenylenediamined KOHb DMFb

$3.23/g $90/250g $70/25kg $50/18L

200g 55g 142g 40L

$646 $20 $0.40 $111

COP-180 $4.74/g 164g $778

21

SI References 1. A. Bettelheim, B. A. White, S. A. Raybuck, R. W. Murray, Electrochemical polymerization of

amino-substituted, pyrrole-substituted, and hydroxy-substituted tetraphenylporphyrins. Inorg.

Chem. 26, 1009–1017 (1987).

2. M. Yuasa, K. Oyaizu, A. Yamaguchi, M. Kuwakado, Micellar cobaltporphyrin nanorods in

alcohols. J. Am. Chem. Soc. 126, 11128–11129 (2004). 3. H. A. Patel et al., Unprecedented high-temperature CO2 selectivity in N2-phobic nanoporous

covalent organic polymers. Nat. Commun. 4, 1357 (2013).

4. H. A. Patel et al., Directing the Structural Features of N2-phobic nanoporous covalent organic

polymers for CO2 capture and separation. Chem. Eur. J. 20, 772–780 (2014).

5. O. Buyukcakir et al., Systematic investigation of the effect of polymerization routes on the gas-

sorption properties of nanoporous azobenzene polymers. Chem. Eur. J. 21, 15320–15327 (2015).

6. U. Jadhav, H. C. Hocheng, Hydrometallurgical recovery of metals from large printed circuit board

pieces. Sci. Rep. 5, 14574 (2015). 7. G. Kresse, J. Furthmuller, Efficient iterative schemes for ab initio total-energy calculations using a

plane-wave basis set. Phys. Rev. B 54, 11169–11186 (1996).

8. A. V. Krukau, O. A. Vydrov, A. F. Izmaylov, G. E. Scuseria, Influence of the exchange screening

parameter on the performance of screened hybrid functionals. The Journal of Chemical Physics

125, 224106 (2006).

9. P. E. Blochl, Projector augmented-wave method. Phys. Rev. B 50, 17953–17979 (1994).

10. S. Grimme, J. Antony, S. Ehrlich, H. Krieg, A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J. Chem. Phys. 132,

154104 (2010).

11. Z. Wang, Comprehensive Organic Name Reactions and Reagents (John Wiley, Hoboken, N.J.,

2009).

12. R. Zhao et al., One step synthesis of azo compounds from nitroaromatics and anilines.

Tetrahedron Lett. 52, 3805–3809 (2011).

13. I. J. P. M. C. Kloetzel, The Wohl-Aue Reaction. I. Structure of benzo[a]phenazine oxides and

syntheses of 1,6-dimethoxyphenazine and 1,6-dichlorophenazine. J. Am. Chem. Soc. 73, 4958–4961 (1951).

14. I. J. P. M. C. Kloetzel, The Wohl-Aue reaction. II. Reactivities of the chlorophenazines and their

oxides. J. Am. Chem. Soc. 74, 971–973 (1952).