Copper nanoparticles encapsulated in zeolitic imidazolate framework-8 as a highly stable and selective catalyst for CO2 hydrogenation to methanol

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Supporting information of

Copper nanoparticles encapsulated in zeolitic imidazolate framework-8 as a highly stable and selective catalyst for CO

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hydrogenation to methanol

Vijay K. Velisojuâ, Jose L. Cerrillo^b, Yerrayya Attadaâ, Hend Omar Mohamedâ, Qingpeng Cheng^b,e, Xueli Yaoâ, Lirong Zheng^f, Osama Shekhahê, Selvedin Telalovic^b, Javier Narciso^d, Yu Han^b,e, Mohamed Eddaoudiê, Enrique V. Ramos-Fernández^d, Pedro Castañoâ,c,*

a Multiscale Reaction Engineering, KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.

b KAUST Catalysis Center (KCC), King Abdullah University of Science and Technology (KAUST), Thuwal, 23955-6900, Saudi Arabia.

c Chemical Engineering Program, Physical Science and Engineering (PSE) Division, KAUST, Thuwal, Saudi Arabia.

d Laboratorio de Materiales Avanzados, Departamento de Química Inorgánica – Instituto Universitario de Materiales de Alicante, Universidad de Alicante, Apartado 99, E-03080 Alicante, Spain.

e King Abdullah University of Science and Technology (KAUST), Physical Sciences and Engineering Division, Advanced Membranes and Porous Materials (AMPM) Center, Thuwal 23955-6900, Saudi Arabia

f Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049 China

*Corresponding author: [email protected]

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Results

Fig. S1. Missing linker replaced by –OH/OH2 in the Zn nodes of the MOF that are active for ion exchange (Cu capture).

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Fig. S2. Using defective nodes to deposit Cu species. A linker missing from the ZIF-8 structure is replaced by–OH/OH2 species, which are active for Cu ion exchange into the MOF.^22,31

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Fig. S3. In situ DRIFT spectra of Cu/ZIF-8|IE|, and Cu/ZIF-8|IM| catalysts before and after adsorption of CO2+H2 (1:3) under 25 bar after reduction at 523 K for 1 h.

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Fig. S4. Powder XRD patterns of ZIF-8 and Cu/ZIF-8|IM| catalysts before and after reduction at 523 K.

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Fig. S5. Powder XRD patterns of ZIF-8 and Cu/ZIF-8|IE| (after ion-exchange), Cu/ZIF-8|IE|R (after reduction at 523 K), and Cu/ZIF-8|IE|R after 3 years storage in a glass vial.

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Fig. S6. Thermogravimetric analysis (TGA) and differential thermal analysis (DTA) profiles of ZIF-8 and Cu/ZIF-8|IE|, and Cu/ZIF-8|IM| materials after preparation carried out in different atmospheres (a) zero air, and (b) 6%H2/Ar.

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Fig. S7. HAADF – STEM – EDX analysis of ZIF-8 sample at different resolutions.

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Fig. S8. (a) TEM and (b) HAADF-STEM-EDX images of Cu/ZIF-8|IM| sample after reduction at 523 K at different resolutions.

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Fig. S9. XPS spectra of ZIF-8 and Cu/ZIF-8|IE| samples before and after reduction at 523 K a) C 1s, b) O 1s, and c) N 1s.

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Fig. S10. CO2 hydrogenation to methanol performance over the Cu/ZIF-8|IE| catalyst under 25 bar.

Reaction conditions: 80%H2/20%CO2 feed; T = 523 K, P = 25 bar, GHSV = 15,750 h⁻¹.

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Fig. S11. (a) Comparison of CO2 to methanol performance of the Cu-loaded ZIF-8 catalysts in this study with that of the commercial Cu-Zn-Al catalyst, and (b) corresponding space-time-yields. Reaction conditions: 80%H2/20%CO2 feed; T = 523 K, P = 50 bar, GHSV = 15,750 h⁻¹. (c) Influence of reaction temperature on product selectivity and (d) their corresponding methanol space-time yields over the Cu/ZIF-8|IE| catalyst. Reaction conditions: 80% H2/20% CO2 feed, P = 50 bar, GHSV = 15,750 h⁻¹.

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Fig. S12. CO2 hydrogenation to methanol performance over the size-specific Cu/ZIF-8|IE| catalysts over time. Reaction conditions: 80%H2/20%CO2 feed; T = 523 K, P = 50 bar, GHSV = 15,750 h⁻¹.

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Fig. S13. Effect of reaction temperature on the thermodynamic equilibrium of CO2 conversion and product selectivity for CO and methanol products at 50 bar with 80%H2/20%CO2.

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Fig. S14. Powder XRD patterns, XPS spectra of (a) reduced and (b) used (100 h time on stream) forms of Cu/ZIF-8|IE| catalyst.

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Fig. S15. (top) Density functional theory (DFT) optimized structures for CO2 adsorption on ZIF–8 without any linker vacancies (left image) and a Cu13 cluster-loaded ZIF-8 with linker vacancies (right image). (bottom) Three different possible connections of the ZIF-8 network in defect-free ZIF-8 (left), fully Cu-exchanged (middle), and partially Cu-impregnated ZIF-8 systems (right).

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Table S1. Physico-chemical characteristics of the catalysts.

Catalyst Element (wt%)^a SBET

(m²/g)^b

Crystallite size (nm)^c

Uptake (µmol/gcat) O/Zn ratio^f

Cu Zn Al CO2d NH3e

ZIF-8 - 27.4 - 1167 62 41 77 0.26

Cu/ZIF-8|IE|R 12.1 19.3 - 880 81 2541 167 0.79

Cu/ZIF-8|IM|R 12.9 14.7 - 25 67 649 1101 0.84

Cu-Zn-Al 43.7 15.6 3.6 79 - - - -

a Determined from ICP-OES analysis

b Obtained from N2-sorption analysis

c Calculated from powder XRD patterns w.r.t. ZIF-8 (110) plane

d Calculated from CO2-TPD analysis

e Calculated from NH3-TPD analysis

f Obtained from XPS analysis

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Table S2. Relative surface compositions obtained from XPS analysis.

Catalyst Cu/Zn O/Cu Cu/O O/(O+Zn+Cu+N)*100

ZIF-8 - - - 13.7

Cu/ZIF-8|IE| 0.97 0.94 1.06 28.9

Cu/ZIF-8|IE|R 0.46 1.69 0.59 31.2

Cu/ZIF-8|IM| 0.45 1.88 0.53 30.6

Cu/ZIF-8|IE|R-Used 0.46 1.02 0.98 20.3

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Table S3. Comparison of the present study with previously reported systems for methanol production.

Catalyst XCO2

(%)

SMeOH (%)

Productivity (gMeOH gmetal-1 h-1)

Ref.

Cu-Zn-Al 23.3 61 1.53 at 523 K, 50 bar (Cu) Commercial

In/Co-ZIF-67 17.3 62 1.133 at 573 K, 50 bar (In) 24

Cu/Zn-ZIF-8 18 55 1.326 at 533 K, 45 bar (Cu) 25

CuZn@UiO-bpy 3.3 100 0.0026 at 523 K, 40 bar (Cu) 27

Pd/ZIF-8 12 78 3.14 at 533 K, 45 bar (Pd) 28

Cu/ZIF-8|IE| 9.5 90 2.2 at 523 K, 50 bar(Cu) This work

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Coordinates from density functional theory (DFT) calculations:

Cu13/ZIF-8 defective linker 1.0

14.7340002060 0.0000000000 0.0000000000 -4.9113281654 13.8913504643 0.0000000000 -4.9113281654 -6.9456641236 12.0302688085 C N H Zn O Cu

44 22 58 6 2 13 Cartesian

-2.100303462 8.019644796 8.883234890 -1.626461780 7.585332992 3.165500720 8.908410131 -2.517739277 5.857525714 4.330911540 0.912181539 6.409366049 4.064027779 -0.707698162 11.415088780 -0.478781548 -1.839054465 8.067233632 2.868601227 10.603636365 0.700678934 3.207498140 5.867634003 3.862883062 8.216224584 7.207983403 5.167590040 7.685836925 2.208150561 2.489724290 -5.470737338 1.216564775 9.532604335 8.138444020 0.812895496 8.856575320 7.666357973 1.018336059 3.176111414 -5.397479850 7.579834329 5.869038828 -2.085338565 3.655741352 11.355996591 -1.616344341 -1.068286290 8.107475034 8.956438239 6.268806148 0.759567120 4.357844857 5.060268587 3.909777345 4.028483957 10.190637025 5.156305668 -0.495372161 7.946861851 2.473122561 2.857305560 -4.676535046 9.558421359 3.183034960 0.484592086 7.093263362 2.450115057 -4.257004503 7.449539592 -0.045629824 7.997476619 4.609974863 S20

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7.180749803 -2.568388453 4.514779425 4.869130066 -0.803079760 7.653079912 7.215364609 5.135917263 0.070942495 -0.107949798 -0.130285339 9.386557160 2.417631982 8.568330454 0.033480238 4.911868803 7.016044323 3.095592758 -4.861497872 5.924109687 4.538322653 7.387077026 2.643417128 4.608074296 9.800836359 0.907556510 7.434128541 2.250478928 -3.509609195 6.173344349 0.650409962 8.281077292 5.898139987 5.876888438 -2.223022374 3.878161815 5.648190086 -1.938238709 8.224854154 5.917363112 4.397043104 0.075646329 0.544286141 0.729166544 10.411836651 2.202706226 7.091652873 0.054677571 5.705048603 8.114287336 2.473639741 -4.090419456 4.816461419 3.900706537 7.299827942 3.394391720 5.893279755 10.566482548 0.904401933 6.154854243 -2.359902342 8.288503192 7.553901924 -1.334433010 7.611234768 4.513720686 7.795963729 -1.804675883 5.446896702 5.385359888 0.094842461 6.774797700 2.967036033 -1.429076531 10.986210235 0.477426185 -1.232112743 8.859715325 2.604219245 9.318874947 1.142201845 3.590366427 7.101921509 3.351284128 8.559501432 6.167659145 4.324653144 7.495945826 3.232624376 3.398659200 -4.421539655 1.275998237 8.632704200 8.485782030 0.614254743 7.533138020 7.467494153 1.298532710 4.515405060 -4.352520673 6.765828648 5.468022004 S21

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-2.374626366 2.370367518 10.940218013 -1.371238683 0.020664497 8.924703181 7.843564107 5.569640824 1.187916833 5.421428861 5.802975514 3.414815994 2.940358217 10.167229404 4.304875198 0.507842117 8.200164306 3.391573214 2.622356623 -3.661626958 8.650268583 3.557568516 -0.609961881 7.876626204 1.742141365 -2.554689947 6.357070871 1.707637769 7.934606076 5.851426403 0.865991890 11.194854680 2.894229969 5.261040138 -2.234644619 9.208148354 5.835633661 3.749366854 0.957019871 0.010296827 1.683627266 10.538660167 -3.306930949 -0.180639863 11.225672388 6.763269101 8.035725297 2.743996061 -3.022999948 5.065734901 3.834648111 6.810129035 2.787889040 6.671481559 10.157795456 0.170007322 5.449711879 -3.107676165 0.686752762 6.328474522 6.746384979 4.339989833 5.771509360 10.273629214 4.606576034 2.888744282 1.700670383 6.778382663 0.977940542 1.594328462 0.942238507 10.146942535 0.896506356 -3.163223757 11.204282492 5.332858579 9.097677029 2.787665905 5.768436382 -1.137468992 3.760794527 0.163559921 7.781954497 6.741209180 -3.248967459 9.801019825 5.452286124 6.712663257 -1.698550089 8.317186372 -1.957579938 7.004145587 9.242843298 -2.615015251 7.321508457 2.811738502 9.584721261 -2.132413453 6.612485455 4.434048998 1.651853610 5.615585043 S22

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4.763833136 -0.264807902 10.713591949 -0.277854618 -2.768511209 7.552698697 3.070221745 11.410071910 1.395450998 2.159390549 5.597641377 3.971372073 7.198179520 7.579612040 5.224096153 7.827699401 2.403170182 1.431060641 -5.338813411 1.471311877 10.578720870 7.119784935 0.675024055 9.203359828 7.787451144 -0.000018201 2.817645283 -5.261675874 8.345825258 6.627920170 -1.902008303 4.456313335 10.645969615 -2.576834650 -1.219681221 7.616868388 9.643907649 6.729464690 1.460318209 4.450040299 3.991336184 4.090604076 4.724969974 9.360149410 5.219548559 -0.330410874 8.065652606 1.407782098 3.042423897 -4.462537783 10.605680171 2.135963495 0.695171447 6.892116587 3.213419221 -3.275630819 5.692819565 0.684725878 9.360081101 6.116453534 5.032876280 -2.572944799 4.493822632 5.560414056 -2.815297337 7.565932038 5.061744995 5.090020228 0.103183620 0.549424005 0.226154608 11.396959355 3.160372017 6.550473357 0.008770066 5.635552974 8.073411403 1.375937916 10.559307564 3.885116113 4.482730791 8.294840159 3.662807280 6.282663716 10.515866250 1.890861173 5.668602660 -0.794387501 2.813408465 7.541919853 -2.003400001 3.762555322 7.402861861 -1.206507715 4.858547005 5.853110776 -2.468488486 6.980673304 6.065132123 7.277622726 0.036671838 6.050274642 S23

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2.388200202 -1.727915660 9.090828750 2.414721397 8.711636390 3.039724112 7.329378717 5.200452365 3.082563780 -2.521663626 1.645521874 9.090167621 -1.804825658 2.788744323 7.536061473 -1.498284236 5.325942783 6.657875347 1.108971582 3.230843997 8.783443815 3.300231001 2.476258801 8.000140489 0.234110367 5.195629439 7.685019911 1.211821454 5.420302565 9.887461503 1.674991515 3.637351710 6.416716630 3.098303185 3.785492717 10.124854939 2.765225859 4.976722768 8.091245817 3.372449642 6.589141472 9.824459186 2.826490345 7.305259596 7.529384212 3.622079847 5.481018670 5.944925635 4.993152599 4.150763437 7.495158226 5.176229412 5.062475378 9.731043491 5.016252227 6.528240210 7.828517221

CO2/Cu 1.0

14.7340002060 0.0000000000 0.0000000000 -4.9113281654 13.8913504643 0.0000000000 -4.9113281654 -6.9456641236 12.0302688085 C N H Zn O Cu

45 22 58 6 4 13 Cartesian

-2.355795645 7.988298780 8.874849592 -1.612145278 7.529337354 3.183353361 8.849557781 -2.532519712 5.910025972 4.274622928 0.723807699 6.268624400 4.028066364 -0.653098498 11.414042590 -0.460309989 -1.802992467 8.036652462

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2.893899541 10.620701855 0.689478772 3.234279847 5.905362488 3.780114989 8.228758778 7.161593301 5.224168217 7.641767321 2.213172033 2.521063214 -5.494424785 1.273539937 9.529224114 8.112526897 0.858590974 8.863011650 7.615138094 1.026184806 3.211191419 -5.378306103 7.491367907 5.937767585 -2.060870332 3.665903665 11.344290588 -1.594552779 -1.030174834 8.052845108 8.927338644 6.316251832 0.758737034 4.377946993 5.086342490 3.810166610 3.978923832 10.180767232 5.202658213 -0.496216709 7.928685229 2.487667046 2.632214013 -4.718104799 9.562619745 3.134309845 0.301059935 6.977170647 2.385216862 -4.261018991 7.435969233 -0.020179608 7.950579332 4.620898554 7.163034778 -2.553413513 4.516391376 4.860726408 -0.867764739 7.659708414 7.219736056 5.130950762 0.078148627 -0.110985348 -0.101467611 9.369871176 2.384956311 8.593884350 0.037702864 4.946336389 7.064455980 3.061354582 -4.863889462 5.879615224 4.549221963 7.347840025 2.657940709 4.643190512 9.771854246 0.910515331 7.435644405 2.272869532 -3.513950223 6.147202496 0.683929792 8.209501998 5.907078497 5.879913477 -2.194656233 3.844164213 5.666342329 -1.941343382 8.311171673 5.937415777 4.365766795 0.085330699 0.519856849 0.760963804 10.409647468 2.137960287 7.121838041 0.059321256

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5.755615887 8.181299300 2.494211651 10.630173298 4.788560442 3.874155602 7.278105179 3.407553465 5.927746673 10.529657087 0.887767215 6.149933778 0.737632196 7.110408037 10.136199543 -2.504491943 8.281037197 7.534929953 -1.305598306 7.538138257 4.530154265 7.761176922 -1.803759072 5.469393381 5.349836459 -0.021677995 6.723981816 2.950995888 -1.408711723 10.990372051 0.473389187 -1.207879573 8.860810276 2.593438765 9.347136332 1.140264976 3.620659414 7.149429617 3.309442607 8.559943326 6.147718083 4.343841308 7.459926305 3.240612220 3.428277718 -4.447918517 1.301203457 8.625017318 8.455253098 0.624443987 7.545132281 7.419019794 1.310764416 4.549438515 -4.343267883 6.680647450 5.504930869 -2.389493367 2.384120414 10.939568357 -1.369770028 0.047058271 8.890200410 7.842812763 5.579476043 1.191261290 5.446555295 5.844323364 3.352198380 2.916184048 10.176112703 4.318096707 0.511874146 8.185154527 3.398130010 2.514931069 -3.685131184 8.652217551 3.538041071 -0.695108977 7.855921817 1.808896568 -2.530067473 6.296353824 1.714077114 7.803353716 5.898404582 0.900990056 11.243161585 2.847035238 5.274364705 -2.204298530 9.300191597 5.872596356 3.706351948 0.960039500 0.012551044 1.728384996 10.490466572 -3.398812174 -0.140590844 11.245377911 S26

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6.811975157 8.087331296 2.777897398 -3.037984409 5.043313963 3.801637183 6.775199239 2.807003610 6.703963655 10.144810093 0.111948549 5.475083610 -3.133907523 0.718897356 6.317839806 6.736390487 4.358861187 5.810090409 10.249367118 4.598977451 2.862758927 1.644621854 6.815806121 0.988960318 1.583868223 0.933133162 10.200922087 0.922703352 -3.190645091 11.210369613 5.377640269 9.156174078 2.831143398 5.773510596 -1.107394069 3.741064624 0.133841131 7.769493684 6.749702755 -3.240279295 9.820015930 5.416760826 6.719273949 -1.652069601 8.406980198 -2.289198130 6.965555494 9.233122834 -2.595964226 7.248453966 2.827690575 9.498497879 -2.161001767 6.696240203 4.359730525 1.338610037 5.377373801 4.710191655 -0.187120179 10.711847342 -0.253180155 -2.732157554 7.520192938 3.123234849 11.433096556 1.373038664 2.182635534 5.639725281 3.878101582 7.218394741 7.554273773 5.288650546 7.799950503 2.398120670 1.464179935 -5.354146505 1.559376363 10.566510057 7.095807650 0.726796980 9.218686984 7.737110578 0.009677997 2.853399324 -5.227375055 8.228138297 6.719590541 -1.866362005 4.465759851 10.635407323 -2.540107549 -1.169783564 7.545793410 9.600427698 6.797205577 1.461533267 4.461827451 4.007338784 3.927137006 4.661687308 9.341313128 5.278569042 S27

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-0.348327475 8.058901611 1.422410837 2.811738607 -4.540253130 10.618396511 2.079919757 0.472638522 6.768073112 -1.651663856 10.550868002 5.686551744 0.776636883 9.289902398 6.104639255 5.014959532 -2.554337382 4.425213983 5.632934696 -2.858284122 7.703330036 5.068429184 5.043234250 0.123586954 0.468961248 0.277163699 11.396574293 -1.829223516 -0.385688951 12.020704664 5.707518523 8.175769750 1.393899101 10.551469011 3.843733799 4.434754106 8.278337348 3.655494095 6.313016145 10.437059159 1.851965314 5.624932636 -0.826070304 2.724218734 7.545589048 -1.951423723 3.780572783 7.408877276 -1.225136258 4.889399313 5.841104684 -2.453081527 6.956724145 6.075021096 7.251611914 0.030163446 6.066985006 2.381903843 -1.758865870 9.112603708 2.406150759 8.739211318 3.035561579 7.341740031 5.203140638 3.082046421 -2.564863587 1.632873954 9.117800958 -1.822079171 2.800975844 7.593914583 -1.446145627 5.300035460 6.700511012 1.110565069 8.038426058 9.318393446 -0.074244317 7.152930682 11.061784046 1.407815965 3.055431540 8.689138248 3.499148672 2.395007397 7.535628369 0.345671312 4.972415928 7.582702634 1.359479700 5.239138917 9.815869526 1.714050921 3.505828721 6.149428250 3.615608928 3.681070967 9.767290869 2.818356148 4.769165144 7.834965024 S28

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3.544474074 6.159406299 10.073737890 2.337262303 7.071406619 8.085363058 3.754160793 5.435850334 5.850187323 5.155212697 4.177184812 7.761363845 5.726264880 5.384990786 9.760614324 4.680896834 6.532643897 7.858664571

Zn-O-Zn 1.0

14.7340002060 0.0000000000 0.0000000000 -4.9113281654 13.8913504643 0.0000000000 -4.9113281654 -6.9456641236 12.0302688085 C N H Zn O Cu

45 22 58 6 4 13 Cartesian

-2.090230062 7.998134043 8.869508213 -1.622169141 7.693026151 3.101270797 8.883283926 -2.516641808 5.881417791 4.324158357 0.893275244 6.416103544 4.057200987 -0.693098638 11.423654778 -0.436554151 -1.876915730 8.047708808 2.898020080 10.591398448 0.693845757 3.215346439 5.873064760 3.837523521 8.213125959 7.210643330 5.181196252 7.668303292 2.209567560 2.489002390 -5.428308376 1.186093949 9.530186409 8.166497568 0.816395817 8.853688437 7.650445890 1.014481358 3.177711175 -5.380422859 7.627877525 5.827305942 -2.033956129 3.630264955 11.352219119 -1.588114220 -1.127067298 8.108834579 8.945196405 6.284308852 0.767483013 4.358930597 5.056615050 3.870943532 S29

(30)

4.014698340 10.194874277 5.175457621 -0.461847580 7.976707387 2.415918570 2.869706311 -4.701692456 9.559576543 3.182101567 0.462060865 7.110995536 2.447492365 -4.260817647 7.457852467 -0.049362528 8.089861103 4.560687034 7.175494069 -2.560484302 4.513865174 4.876605284 -0.818012947 7.661789322 7.220850992 5.127755820 0.077643352 -0.088255261 -0.183968001 9.392198987 2.435626599 8.555169154 0.038015650 4.927275182 7.023414045 3.095171486 -4.847201089 5.985919424 4.476980330 7.386256338 2.643111606 4.613848779 9.825614438 0.870876588 7.423962782 2.248926720 -3.511824977 6.181729648 0.657477381 8.316972438 5.853796644 5.877060505 -2.214069381 3.865926981 5.662315304 -1.944079740 8.244282892 5.926409704 4.383603129 0.077366657 0.554142915 0.706766946 10.399265157 2.196783286 7.082171831 0.074419244 5.724315918 8.126845250 2.486367912 10.646306850 4.867929167 3.848302366 7.308496217 3.393148291 5.896539868 10.584546970 0.880856397 6.141163418 -3.992082165 4.349716085 8.091378473 -2.361567591 8.285106773 7.545132281 -1.354471074 7.764032425 4.453172507 7.778101689 -1.801703082 5.458205095 5.380635384 0.082805577 6.781185987 2.971255128 -1.430007183 10.993788841 0.508578789 -1.269821024 8.853303376 2.617190147 9.314213937 1.141684576 S30

(31)

3.606009341 7.113791354 3.353028376 8.557090153 6.181481595 4.325398886 7.489413374 3.232179957 3.402966220 -4.379493866 1.219939231 8.622154098 8.501842965 0.612046077 7.527050182 7.461846648 1.297525878 4.518472642 -4.328975726 6.854782110 5.372080465 -2.331701578 2.346244882 10.935658946 -1.363782941 -0.061308040 8.958050769 7.841702955 5.571613410 1.194172643 5.426958969 5.804003860 3.397107482 2.939793090 10.177224268 4.306787955 0.529560203 8.224480852 3.346423896 2.629915200 -3.678317342 8.662888120 3.565982112 -0.625985522 7.893985507 1.755304198 -2.548119026 6.357142577 1.703139223 7.939015892 5.793067766 0.872966374 11.208384420 2.878518470 5.274762115 -2.229365756 9.229417785 5.843938383 3.731398301 0.955732659 0.018022296 1.660963920 10.489612553 -3.332892572 -0.192287566 11.260476325 6.783892671 8.048011630 2.755364687 -3.016428533 5.102407949 3.797354184 6.818522579 2.788882633 6.678278569 10.193952787 0.130854614 5.443516123 -3.078286822 0.710041172 6.303776828 6.756512412 4.339121487 5.780447870 10.278309350 4.649472442 2.837711846 1.699506329 6.782674984 1.005802621 1.599922394 0.932876021 10.146677940 0.907645190 -3.172683946 11.202839050 5.346159157 9.106588275 2.803004533 5.767906378 -1.127925598 3.753167161 S31

(32)

0.146021054 7.797804627 6.672973760 -3.262350784 9.800783242 5.467877516 6.724023275 -1.687756820 8.336387085 -1.933116997 6.982273404 9.215065831 -2.611277683 7.446085851 2.732771743 9.550189619 -2.134635847 6.647228442 4.414684213 1.630884383 5.625269654 4.750704865 -0.239053295 10.723384836 -0.232154876 -2.799982171 7.518953858 3.086036448 11.409682900 1.384888437 2.163226129 5.608650280 3.929422635 7.189113003 7.548745285 5.283020191 7.806939904 2.403107723 1.433334348 -5.289253198 1.449426466 10.572067988 7.144311438 0.702584498 9.204779607 7.767265559 0.000398588 2.817861835 -5.243332173 8.393896187 6.581712113 -1.850174323 4.425579204 10.638354439 -2.538600052 -1.259313548 7.604477592 9.622562984 6.754851310 1.472745484 4.441789124 3.982063672 4.014608992 4.708257123 9.362601728 5.242466152 -0.272378711 8.023096608 1.348893912 3.059392970 -4.500801431 10.607568907 2.132638124 0.657233824 6.897554769 -1.699073096 10.590110752 5.690786342 0.725588633 9.385529748 6.106540181 5.027193805 -2.566707650 4.472553202 5.593595260 -2.833446515 7.599172066 5.068684522 5.074746765 0.107237820 0.556137228 0.236441541 11.394252454 3.145318726 6.525830203 0.011344544 5.655708971 8.090663912 1.389074991 10.537245488 3.947536926 4.442730322

S32

(33)

8.307545578 3.657146725 6.274350841 10.496972315 1.862536483 5.652506099 -0.445948530 2.262803600 7.499657776 -1.419762366 3.401463371 7.241848929 -1.065296814 4.966294748 5.719899691 -2.463601978 7.052304215 5.984733933 7.269592480 0.038297184 6.054461554 2.420654046 -1.751135358 9.103809686 2.432382593 8.720297776 3.039327219 7.337158389 5.201868855 3.090744358 -2.457074538 1.602882908 9.072687135 -1.424516666 2.434487073 7.446868544 -1.281380282 5.519108737 6.488886558 -4.116952011 4.312293292 9.248979179 -3.856647922 4.374177108 6.917103973 1.160923048 3.278999098 8.879601548 3.266170006 2.471181137 7.976212917 0.218742939 5.158393572 7.729303380 1.233838941 5.446418645 9.957068659 1.671705696 3.653105050 6.440488600 3.197968615 3.875786594 10.145041609 2.787051259 4.970437100 8.102181698 3.439213870 6.547308583 9.838474122 2.784979160 7.288062248 7.511892252 3.637433072 5.443178322 5.935806785 5.008883778 4.120980286 7.525763059 5.311512561 5.111331680 9.711819115 4.999342475 6.527726417 7.800703185

CO2/Cu-Zn 1.0

14.7340002060 0.0000000000 0.0000000000 -4.9113281654 13.8913504643 0.0000000000 -4.9113281654 -6.9456641236 12.0302688085

S33

(34)

C N H Zn O Cu 45 22 58 6 4 13 Cartesian

-1.867766329 8.197349412 8.839216017 -1.649687223 7.701451003 3.170120020 8.867867508 -2.532943319 5.924137352 4.355664999 0.879196472 6.350670394 4.029004773 -0.591573101 11.433170162 -0.470560187 -1.751080850 8.056454788 2.927036462 10.453652224 0.883105964 3.287680690 5.824042575 3.771597393 8.277680217 7.217006287 5.255038004 7.649993501 2.233287104 2.531625686 -5.473355248 1.340635204 9.534854469 8.143463497 0.892298001 8.872648218 7.619700059 1.038721803 3.212310391 -5.326908904 7.569159354 5.956270240 -2.005401592 3.595509053 11.545593682 -1.638106400 -1.031425022 8.135204457 8.959188295 6.332685568 0.777335775 4.440581662 5.019288381 3.767266709 3.994512308 10.168660614 5.235464779 -0.495117025 7.982583783 2.475444401 2.977760716 -4.492578866 9.500038342 3.194851735 0.463192658 7.036973443 2.443519180 -4.151166289 7.401634971 -0.044382302 8.041894298 4.611671068 7.183352228 -2.568916413 4.528373805 4.882666303 -0.788187944 7.673602884 7.233698696 5.171847256 0.094028580 -0.151764037 -0.071309304 9.422996710 2.389558456 8.488121860 0.087520208 4.991716546 7.032554636 3.102053109 -4.800523701 5.938536000 4.596296587 S34

(35)

7.401639332 2.660051889 4.659359137 9.808649717 0.952737815 7.449876610 2.214503309 -3.459968548 6.098504090 0.672977756 8.348769518 5.881297684 5.904033812 -2.208179417 3.849180764 5.662325023 -1.892077835 8.303989601 5.948603519 4.411260857 0.090864620 0.480433973 0.802603409 10.450537808 2.132184438 7.017257736 0.050045918 5.783547015 8.160309089 2.532347586 -4.023605444 4.868109107 3.912496077 7.331255338 3.401643091 5.948017598 10.556355419 0.911271349 6.160159052 -3.580364448 4.866710779 8.553099796 -2.230719547 8.415477345 7.520012956 -1.352089178 7.742626481 4.513323793 7.782373955 -1.806578993 5.471799475 5.402373089 0.067685242 6.766520678 2.944670000 -1.331996457 11.006528844 0.463983684 -1.134373187 8.867342692 2.599803620 9.165542284 1.235412371 3.668907967 7.094079845 3.364962404 8.614238859 6.191309056 4.390158000 7.504093214 3.254378593 3.450822440 -4.423258686 1.374189041 8.634569273 8.496769111 0.642002749 7.559664217 7.453423573 1.313764640 4.555766569 -4.288707781 6.758911489 5.540877082 -2.360628880 2.355219135 11.037627015 -1.429825957 0.034284978 8.991723902 7.882590309 5.582511001 1.208211959 5.498507534 5.803795774 3.339385953 2.933378627 10.152754747 4.348545221 0.515857579 8.181327766 3.395062069

S35

(36)

2.599779345 -3.519192203 8.591861903 3.568530407 -0.577977077 7.878971707 1.752008166 -2.471682409 6.228022318 1.723093771 7.985218543 5.832382726 0.926627488 11.226616715 2.853627887 5.261782169 -2.151185321 9.290339194 5.874919753 3.736642159 0.952520589 -0.032598526 1.766822352 10.530383145 -3.423295226 -0.221639793 11.241973311 6.843535429 8.077184106 2.801464647 -2.962772127 5.146971385 3.832482590 6.826322176 2.783909354 6.718676290 10.163796977 0.117317470 5.511451095 -3.104272480 0.752805988 6.315890838 6.789025273 4.363764332 5.811702718 10.318213949 4.676484091 2.902951927 1.664738709 6.693457807 0.988298651 1.532952432 1.002423430 10.209920472 0.934952054 -3.123126529 11.201287332 5.402319876 9.132002627 2.865694212 5.804943038 -1.119910257 3.745660260 0.155676828 7.920250195 6.747091940 -3.331482772 9.832913941 5.430054399 6.722244882 -1.629134930 8.402553070 -1.559531219 7.216217934 9.173633393 -2.661471431 7.495726766 2.814854307 9.518211761 -2.151979163 6.704264103 4.454294199 1.516787570 5.478945336 4.695153445 -0.096847415 10.733778619 -0.236830452 -2.645316127 7.490635012 3.148896667 11.195151809 1.644441533 2.237431401 5.546333267 3.846582139 7.261142632 7.595996811 5.343761260 7.774426559 2.429035872 1.471843243 S36

(37)

-5.346916750 1.642780113 10.569661535 7.128118942 0.745904902 9.224906044 7.718182267 0.022958002 2.845748115 -5.169082671 8.332455379 6.708053765 -1.771529123 4.436323855 10.911742848 -2.598243079 -1.207950025 7.661536917 9.643932203 6.790468353 1.482177242 4.534599187 3.939305757 3.853355128 4.673091689 9.325810533 5.332561143 -0.335125863 8.063944156 1.409466292 3.181610816 -4.247965112 10.541547051 2.149154807 0.663547580 6.817637727 -1.737440334 10.580359003 5.573009970 0.738887995 9.431156015 6.033576468 0.122368252 11.331755281 4.427319271 5.608466796 -2.795911838 7.677175993 5.083222198 5.091972033 0.139767668 0.451186959 0.323748474 11.443528810 -1.835662218 -0.487082045 11.972872466 5.720308053 8.144305480 1.433984005 -4.068873130 3.916684215 4.467031123 8.320884834 3.661800506 6.348697762 10.444205189 1.861258446 5.613840795 -0.647381051 2.673890760 7.648760344 -1.756743716 3.551010845 7.052312071 -0.901729834 5.230077488 5.421139911 -2.386125231 7.061520623 6.052259463 7.292110802 0.034637082 6.079808905 2.372729043 -1.603581501 9.109704635 2.428571026 8.638644692 3.134125765 7.412817354 5.222476903 3.114600582 -2.532704271 1.683938962 9.148622344 -1.647245457 2.661054705 7.480601910 -1.311054758 5.357726056 6.303512233 S37

(38)

-4.567415336 4.487218922 8.031672481 -2.601839998 5.240624482 9.084164396 1.353737501 3.177841724 8.553966004 3.586914954 2.484204299 7.676117613 0.366244847 5.048915290 7.367865752 1.336352663 5.462539161 9.491725467 1.877583497 3.635913651 6.139286872 3.202796680 3.831958994 10.067518112 3.144674526 4.783590898 7.959731295 3.488882409 6.540786000 9.730574534 2.249594103 6.887227444 7.574618501 3.737393140 5.411659138 5.798204424 5.382175044 4.239341106 7.299437443 5.336972501 5.130814118 9.557218133 4.826625651 6.630341430 7.639545407

CO2/Cu-O-Zn 1.0

14.7340002060 0.0000000000 0.0000000000 -4.9113281654 13.8913504643 0.0000000000 -4.9113281654 -6.9456641236 12.0302688085 C N H Zn O Cu

45 22 58 6 4 13 Cartesian

-2.017325821 8.219485354 8.914465000 -1.659220381 7.661673204 3.208701428 8.875342346 -2.539729327 5.906104013 4.375742149 0.873667561 6.334646256 4.027968471 -0.592435047 11.422199146 -0.469126207 -1.728590609 8.045699606 2.887863662 10.470494715 0.888603752 3.289006505 5.833668774 3.771068202 8.267533318 7.191258735 5.263880070 7.654188220 2.250657993 2.520738386 S38

(39)

-5.475501171 1.337995983 9.528598121 8.144176012 0.881115587 8.862975797 7.629478612 1.045778537 3.202108779 -5.343759687 7.531888485 5.978454281 -2.024988260 3.610900548 11.553148625 -1.629148246 -0.996231371 8.110698935 8.961368966 6.327205408 0.765389736 4.445482549 5.034180389 3.772319472 3.991649316 10.158026740 5.223205923 -0.504865716 7.949689151 2.503041706 2.868120097 -4.457183747 9.540989633 3.211446763 0.465470851 7.016738729 2.426766887 -4.138330594 7.418741869 -0.048297072 8.044964921 4.639701657 7.183607670 -2.572055846 4.517787133 4.889271488 -0.798870675 7.656279434 7.222638586 5.184377180 0.085655516 -0.146547878 -0.043637924 9.409378308 2.363685351 8.505563000 0.081252438 4.983087783 7.044417629 3.080927808 -4.807586204 5.926047646 4.593409345 7.403961624 2.667400494 4.654258331 9.809696693 0.959343504 7.441972459 2.238136600 -3.494849985 6.084765940 0.668552446 8.335551735 5.910110226 5.899789813 -2.207950196 3.849746166 5.666750410 -1.900593091 8.293499015 5.934469453 4.428736069 0.090768377 0.481553701 0.821481554 10.445966551 2.119046746 7.032537799 0.035729899 5.773906332 8.174429701 2.514049472 -4.042401213 4.841403358 3.913975731 7.332154190 3.404059989 5.945033911 10.562003221 0.924134568 6.155395623

S39

(40)

-3.210997993 4.935389704 8.699316197 -2.311029626 8.408629100 7.575929287 -1.354225711 7.721643411 4.551159101 7.793051645 -1.808752894 5.455017047 5.416684170 0.055314657 6.750340221 2.934184991 -1.320633558 10.997722632 0.462991890 -1.116669131 8.861796950 2.557364953 9.181454833 1.232801825 3.661398635 7.099691523 3.346989298 8.613349365 6.179946350 4.384070520 7.501648118 3.265005414 3.446491398 -4.425036340 1.382551724 8.627783735 8.501312255 0.638071448 7.550040556 7.462082183 1.321571533 4.546503231 -4.298535372 6.734782037 5.553172150 -2.371522690 2.375069756 11.036087488 -1.418814462 0.068485457 8.969107115 7.880625262 5.585921427 1.198479395 5.498021149 5.820193881 3.329918253 2.925697606 10.145746020 4.341074533 0.511564589 8.179737638 3.422070130 2.572840631 -3.495569875 8.601185115 3.577031807 -0.578769066 7.859411030 1.772198992 -2.503889186 6.147406858 1.721390192 7.974140278 5.855998018 0.908686364 11.226165152 2.855805418 5.265705954 -2.152449460 9.282784251 5.867139584 3.756395806 0.955046970 -0.030585214 1.785965040 10.526220612 -3.418256263 -0.212972014 11.216276752 6.831262228 8.093082517 2.788267518 -2.980290844 5.105567589 3.834251218 6.827686917 2.782443808 6.712601358 10.172711077 0.132570260 5.501369591

S40

(41)

-3.099390589 0.766336155 6.315024629 6.789300449 4.366112097 5.814012368 10.299733079 4.646805449 2.905947445 1.639744919 6.696284848 0.963119272 1.536729062 1.023475473 10.218282107 0.908926969 -3.109443386 11.204438811 5.388931340 9.143511869 2.852713635 5.802840775 -1.120174075 3.746189451 0.155072763 7.884452110 6.769468511 -3.285728602 9.755594686 5.446126580 6.725010226 -1.633080307 8.392255373 -1.779116758 7.241402563 9.283205165 -2.654006233 7.435751008 2.857838462 9.530622640 -2.159432223 6.682381586 4.481296661 1.514238386 5.465050508 4.695477200 -0.105786398 10.719258157 -0.243333149 -2.637238363 7.498418697 3.100790703 11.216114010 1.648002452 2.242470465 5.553105612 3.864374905 7.248928261 7.562428273 5.343677005 7.778596658 2.450685659 1.467596546 -5.352663319 1.638508511 10.562407757 7.131773179 0.723067300 9.215402132 7.730529488 0.037898222 2.831227473 -5.205298778 8.274256904 6.755874489 -1.770079610 4.452083403 10.931796862 -2.582556266 -1.151863745 7.618215743 9.652963899 6.778674673 1.469569536 4.541715518 3.953891824 3.859442608 4.664084265 9.311655015 5.320747222 -0.342988814 8.019151320 1.435078776 3.046599160 -4.195900507 10.579033508 2.167582236 0.675584040 6.799772896 -1.700630126 10.513270579 5.579903426

S41

(42)

0.738337970 9.420585127 6.084681327 5.034629302 -2.555608384 4.438411112 5.617788382 -2.812484245 7.677657140 5.070806443 5.110878128 0.147731705 0.440804555 0.334528054 11.433760303 -1.842547998 -0.463793198 11.973461889 5.716801118 8.165955409 1.415204744 -4.108247396 3.897069577 4.475524698 8.322490796 3.663967352 6.347061431 10.453394687 1.875754047 5.611037808 -0.621066246 2.654386626 7.622558975 -1.756144574 3.572154023 7.122857141 -1.035789751 5.112459874 5.517117302 -2.405859122 7.042197904 6.117752846 7.302788420 0.030753801 6.065433288 2.370676368 -1.568894568 9.098251754 2.412531012 8.639672633 3.125969208 7.409045272 5.233270764 3.103484361 -2.537463387 1.697607817 9.146962350 -1.624186879 2.659408694 7.514972025 -1.333784355 5.336041544 6.418160789 -4.266821718 4.627563289 8.280602693 -2.159726704 5.261781292 9.121313835 1.398763844 3.146524262 8.532371745 3.621480463 2.467409374 7.680713250 0.465380058 5.064008661 7.323871259 1.362628246 5.392075650 9.502251906 1.939981954 3.601345506 6.120050306 3.284570152 3.791222312 10.028576740 3.132190389 4.767935261 7.937475190 3.501514047 6.481261875 9.736517526 2.399012101 6.920900479 7.535423290 3.801530203 5.421160524 5.804387990 5.406672007 4.241668637 7.357603908 S42

(43)

5.407214212 5.160013604 9.599108055 4.908384547 6.629924982 7.672388184

S43