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Supplementary Information

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Supplementary Information Internally hollow Cu O nanoframes with the abundance of {110} 2 facets enhance direct propylene epoxidation Yueming Qiu 1,†,Yichen Zhang1,†,Ronghui Zhang1,Meng Huang1,KokBing Tan1,2, Guowu Zhan2,Gang Fu1,3,,Qingbiao Li1,4,& JialeHuang1,* 1Department of Chemical and Biochemical Engineering, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, Fujian 361005,China 2College ofChemical Engineering, Integrated Nanocatalysts Institute(INCI), Huaqiao University, Xiamen 361021,China 3StateKey Laboratory ofPhysical Chemistry ofSolidSurfaces, Xiamen University, Xiamen, Fujian 361005,China 4College ofOcean Food andBiology Engineering, JimeiUniversity, Xiamen, Fujian 361021,China † These authors contributed equally to this work: Yueming Qiu and Yichen Zhang. *Corresponding Authors. E-mail: gfu@xmu.edu.cn (G. Fu); kelqb@xmu.edu.cn (Q.B. Li); cola@xmu.edu.cn (J.L.Huang) 1

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Table of contents 1.Supplementary Methods…3 2.Supplementary Figures…9 3.Supplementary Tables…26 4.Supplementary References…32 2

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1.Supplementary Methods 1.1 Synthesis of c-Cu O. Typically, 0.25 g CuSO ·5H O was dissolved in 40.0 2 4 2 mL deionized water to form a clear solution. Then, 1.0 mL OA and 20.0 mL ethanol were added to the above solution successively under intense agitation. During the process of dropping the, 0.8 mol L–1 NaOH solution, the mixture was stirred for 5 min while heating at 100 °C. After that, 30.0 mL glucose solution was added to the above solution and stirred for 60 min. The brick red product was washed with cyclohexane and ethanol for several times, and dried undervacuum at 60°C overnight. 1.2 Synthesis of o-Cu O. o-Cu O was synthesized according to the method 2 2 reported by Hua et al.1. 0.48 g Cu(NO ) ·3H O was accurately weighed and dissolved 3 2 2 in 20.0 mL deionized water at 55 °C. Then 0.70 g PVP was added to the above solution. After adequately stirring, 6.0 mL 1.0 mol L–1 NaOH solution was added dropwise (~195 s), and continued to be mixed for 10 min. The freshly prepared 0.6 mol L–1 ascorbic solution was poured at a constant rate for 3.5 min (about 1 drop every 3 seconds), and was kept stirring at 55 °C for 30 min. After centrifugation, the obtained product was washed with ethanol for several times and stored in an ethanol solutionfor futureuse. 1.3 Synthesis of r-Cu O. r-Cu O was synthesized according to the method 2 2 reported by Zhan et al.2. First, 0.25g CuSO ·5H O was dissolved in 15.0 mL 4 2 deionized water and transferred into conical bottle for adequately stirring at 80 °C. 3

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Then, the mix solution containing 2.0 mL OA and 5.0mL ethanol was poured into the about conical bottleandkept stirring for 30min.After that, 5.0mL1.0mol L–1 NaOH solution was added dropwise (~195 s) with 10 min stirring. A fresh glucose solution (2.0 mol L–1) was added to the above solution at the rate of about 1 drop every 3 seconds, and the mixture was stirred at 80 °C for 3 h. The obtained product should be washed with ethanol and cyclohexane for several times and stored in an ethanol solutionfor futureuse. 1.4 Synthesis of d-Cu O. First, 0.35g Cu(NO ) ·3H O was dissolved in 7.0 mL 2 3 2 2 deionized water using ultrasonication for 5 min to obtain clear solution. 104.0 mL deionized water was added to a beaker in a 33 °C water bath. Then, under intense agitation, 7.5 mL of Cu(NO ) solution was added and 1.31 g SDS was mixed with 3 2 the about solution. After completely mixing, 3.0 mL 1.0 mol L–1 NaOH was added, immediately forming a blue precipitate. Finally, 40.0 mL NH OH·HCl solution was 2 quickly injected into theabove and the precursor was growing in the water bathfor 80 min. The original product was washed with deionized water and ethanol for several times,and dried under vacuum at 60°C overnight. 1.5 Synthesis of c-Cu O-NF. c-Cu O-NF was synthesized according to the 2 2 liquid reduction method. First, 0.17 g CuCl ·2H O and 0.23 g NaCl were dissolved in 2 2 0.0 mL deionized water. After well-mixed, 1.8 mL NaOH solution (1.0 mol L–1) was added into the above solution, and 5.0 mL AA solution (0.1 mol L–1) was added 4

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subsequently with intense stirring for 5 minutes. The mixture gradually transitions from blue to yellow colors as the reaction progresses. After 10 min, the product was washed with ethanol for several times, and was dried under vacuum at room temperatureovernight. 1.6 Synthesis of o-Cu O-NF. In a typical procedure, the Fehling solution 2 consisted of 7.0 g L–1 CuSO ·5H O solution, 25.0 g L–1 SPTT solution and 4.5 g L–1 4 2 KOH solution should be prepared first. Then, 0.4 mL PdCl solution (0.027 mol L–1) 2 and 4.0 mL glucose solution (0.25 mol L–1) were added to a mixture of 20.0 mL Fehling solution and 180.0 mL deionized water under stirring. After that, a clarified light blue solution was aged at 75 °C for 3 h, and the o-Cu O-NF product was 2 thoroughly washed anddried under vacuum at room temperature overnight. 1.7 Synthesis of d-Cu O-NF. d-Cu O-NF was synthesized according to the 2 2 method reported by Lv et al.3. Typically, quantitative Cu(NO ) ·3H O was dissolved 3 2 2 in deionized water with ultrasonication for 3 min to obtain 0.1 mol L–1 Cu(NO ) 3 2 solution. Next, 7.5 mL of Cu(NO ) solution and 1.31 g SDS were successively added 3 2 to 104.0 mL of deionized water with vigorous stirring. After complete dissolution, 3.0 mL NaOH solution (0.1 mol L–1) was added dropwise to formed a blue precipitate of Cu(OH) . Then, 42.0 mL of NH OH·HCl (0.1 mol L–1) was introduced into the 2 2 mixture and the bluesolution changed yellow quickly. After the nanocrystals grew for about 2 h, the precursor was washed with a Soxhlet extractor using ethanol as a 5

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solvent for 16 h. The obtained product was washed with ethanol and deionized water forseveral times and dried under vacuum at 50°C overnight. 1.8 Synthesis of truncated 26-facet polyhedral Cu O-1 (t-26-Cu O-1). 2 2 Typically, 2.72 g Cu(CH COO) was dissolved in 50.0 mL deionized water with 3 2 vigorous stirring for 2 min at 70 °C to obtain clear solution. Subsequently, 30.0 mL NaOH solution (3.0 mol L–1) was added dropwise to formed a black precipitate with vigorous stirring for another 5 min. Then, 0.6 g glucose powder was accurately weighed and was introduced into the mixture with stirring. Next, the reaction system was cooled down to room temperature after the black precipitates turned into brownish-red color and then dark-red color. The obtained product was washed with ethanol and deionized water for several times and dried under vacuum at 70 °C overnight. 1.9 Synthesis of truncated 26-facet polyhedral Cu O-2 (t-26-Cu O-2). The 2 2 preparation scheme for t-26-Cu O-2 is similar to that of t-26-Cu O-2, except that the 2 2 addition quantities of deionized water, NaOH solution (9.0 mol L–1) were 40.0 mL and 10.0mL,respectively.Besides, the timefor crystal growth increased to 70min. 1.10 Synthesis of the spherical Cu O nanocrystals (s-Cu O-3). The 2 2 preparation scheme for t-26-Cu O-2 is similar to that of s-Cu O-NF, except that the 2 2 timefor facet etching was only 3min. 1.11 Computational details. Periodic density functional theory (DFT) 6

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calculations were executed utilizing the Vienna Ab Initio Simulation Package (VASP)4–7. The exchange-correlation effects were incorporated through the Perdew- Burke-Ernzerhof (PBE) functional within the generalized gradient approximation (GGA)4. The projector augmented wave (PAW) method8,9 was used to model core electron interactions using pseudo-potentials, while valence electrons were treated with a plane-wave basis set with a cutoff energy of 400 eV. To more accurately capture the electronic characteristics of Cu(I) species, we implemented the DFT+U10 approach in accordance with Dudarev’s formulation, a widely-accepted method for enhancing electron correlation treatment in transition metal oxides and rare earth metal oxides. A Hubbard U correction (U-J) of 6 eV was applied to the Cu 3d electrons, in line with established methodologies11. The Brillouin zone sampling for all structural models was conducted using the Monkhorst-Pack scheme, adopting a 3×3×1 k-point mesh12. The optimized lattice parameter for bulk Cu O was determined 2 tobe 4.24Å,which isclose tothe experimentallyreported valueof4.27Å13. The Cu O{111}, Cu O{100} and Cu O{110} surfaces were modelled by (2×2), 2 2 2 (2×3) and (2×2) supercells, respectively, each comprising symmetric slabs with eleven layers for the {111} and {100} surfaces, and seven layers for the {110} surface, separated by a vacuum layer of 15 Å. The structural relaxation process allowed the remaining atoms to fully optimize while keeping the lower four layers of each slab fixed. The optimization continued until the Hellman-Feynman forces on the 7

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atoms were reduced toless than 0.03eV/Å. Theadsorption energies (ΔE ) were calculated using Equation (1): ads E =E –E - E (1) ads ad/surf surf ad where E is the total energy of the adsorbed system, E is the total energy of ad/surf surf theclean surface, and E is thetotal energy ofthegas-phase adsorbate(s). ad Given the known limitations of GGA functionals in accurately describing molecular oxygen in triplet state, we referenced gas-phase H O and H to calibrate the 2 2 total energy of O , see Equation (2), analogous to the methodology employed by 2 Nørskov et al.14.In Equation (2), E denoted as thereaction heat at 0 K without zero- r point energy correction, which can be derived from the experimental atomic energies (AE)15, see Equation (3). Here, AE(H O), AE(H ) and AE(O ) denoted the atomic 2 2 2 energies of H O, H and O , respectively. According to our calculations, the corrected 2 2 2 totalenergy ofO should be-9.41 eV. 2 E(O )=2×E(H O)- 2×E(H )- E (2) 2 2 2 r E = 2×AE(H O) -2×AE(H )-AE(O ) (3) r 2 2 2 VESTA packages were usedto visualizetheWulff construction16. 8

Table (Page 8, #1):

VESTApackageswereusedtovisualizetheWulffconstruction16

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2.Supplementary Figures SupplementaryFig.1|Microscopiccharacterizations.SEMandTEMimagesofr-Cu O. 2 SupplementaryFig.2|Photographsofvariousas-preparedCu Ocatalysts. 2 9

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Supplementary Fig. 3 | Characterizations of different catalysts. (a) XPS patterns of C of s- Cu O,s-Cu O-NCands-Cu O-NF.(b)InsituDRIFTSspectraofCOadsorptiononthes-Cu O,s- 2 2 2 2 Cu O-NCands-Cu O-NFat30°C. 2 2 Supplementary Fig. 4 | Microscopic characterization of s-Cu O-NF. (a) TEM image of s- 2 Cu O-NF. The (b,c) HRTEM images (inset is the Fast Fourier transform image) of the area 2 markedwithyellowrectanglein(a). 10

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cc | Top (a) and side (b) view of the structure of Cu O{110} facet. The orange and red balls 2 representCuandOatoms,respectively. Supplementary Fig. 6 | Structural characterizations. XRD patterns of s-Cu O-NF during the 2 HCletchingprocessatdifferenttimes. 11

Table (Page 11, #1):

Top(a)andside(b)viewofthestructureofCu2O{110}facet.Theorangeandredballs
representCuandOatoms,respectively.

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Supplementary Fig. 7 | Characterizations of different catalysts. (a) The UV-vis spectroscopy and (b) photographs for the s-Cu O, s-Cu O-NC and s-Cu O-NF at different HCl-etching 2 2 2 processes. 12

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Supplementary Fig. 8 | Microscopic characterizations. (a,b) High-angle annular dark-field imageofs-Cu O-NCandelementalmappingimagesof(c)Oand(d,e)Cu. 2 Supplementary Fig. 9 | Physicochemical properties of various catalysts. (a) N 2 adsorption/desorptionisothermsand(b)poresizeanalysisofallas-preparedCu Onanocatalysts. 2 13

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Supplementary Fig. 10 | Catalytic performance of propylene epoxidation with O . Propylene 2 conversion and product selectivity over (a) c-Cu O, (b) o-Cu O and (c) r-Cu O nanocrystals at 2 2 2 different temperatures. Reaction conditions: C H : O : N = 10: 5: 85 vol.%, GHSV = 36,000 h-1, 3 6 2 2 50.0 mg catalyst. (d) Facet-controlled selectivity of Cu O catalysts in the DEP reaction. The 2 orangeandredballsrepresentCuandOatoms,respectively. 14

Table (Page 14, #1):

orangeandredballsrepresentCuandOatoms,respectively.

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Supplementary Fig. 11 | Structure characterizations. XRD patterns of t-26-Cu O-1 and t-26- 2 Cu O-2. The SEM, TEM images and simulated structures of (b, c, d) t-26-Cu O-1 and (e, f, g) t- 2 2 26-Cu O-2. The red, blue and yellow colors represent the {100}, {111} and {110} facets, 2 respectively. According to Steno’s law, the angles between two corresponding facets on the crystals are constant. The Miller indices of exposed facets of the obtained two type 26-facet Cu O 2 polyhedrons can be identified by a conjunction of the angle between the facets. If the indices of two crystal planes are (h k l ) and (h k l ), then the cosine of the angle θ between their normals 1 11 2 22 satisfiesthefollowingEquation(4): (4) h1h2+k1k2+l1l2 cosθ= 2 2 2 2 2 2 h1+k1+l1∙ h2+k2+l2 Based on the above Equation (4), the θ ({100} vs {110}) , θ ({100} vs {111}) and θ ({110} vs {111}) are 45o, 54.7o and 35.3o, respectively. Based on the aforementioned results and TEM/SEM observations, the equilibrium crystal morphology was determined through Wulff construction analysis, which was performed using the VESTA software package to accurately representthesurfaceenergy-dependentfacetingbehavior16.Furthermore,thefinestructuresofthe two26-facetCu Opolyhedronscanbealsoseeninsomeotherimportantresearches17,18. 2 15

Table (Page 15, #1):

Basedontheaforementionedresultsand
TEM/SEMobservations,theequilibriumcrystalmorphologywasdeterminedthroughWulff
constructionanalysis,whichwasperformedusingtheVESTAsoftwarepackagetoaccurately
representthesurfaceenergy-dependentfacetingbehavior16.Furthermore,thefinestructuresofthe
two26-facetCu2Opolyhedronscanbealsoseeninsomeotherimportantresearches17,18

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Supplementary Fig. 12 | Catalytic performance of propylene epoxidation with O . Propylene 2 conversion and product selectivity over (a) t-26-Cu O-1 and (b) t-26-Cu O-2 at different 2 2 temperatures. Reaction conditions: C H : O : N = 10: 5: 85 vol.%, GHSV = 36,000 h-1, 50.0 mg 3 6 2 2 catalyst. Supplementary Fig. 13 | Catalytic performance of propylene epoxidation with O . Propylene 2 conversion and product selectivity over as-prepared Cu O nanocatalysts at 225 °C. Reaction 2 conditions:C H :O :N =10:5:85vol.%,GHSV=36,000h-1,50.0mgcatalyst. 3 6 2 2 16

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SupplementaryFig.14|TheHRTEMimages,simulatedstructuresandtheirexpansionfiguresof (a) o-Cu O-NF and (b) d-Cu O-NF. The red, blue and yellow colors represent the {100}, {111} 2 2 and{110}facets,respectively. According to the Gibbs-Wulff’s law of crystal growth, the surface of o-Cu O-NF contains 8 2 similar {111} facets. Besides, based on Steno’s law, the angles between two corresponding facets on the crystals are constant. The Miller indices of exposed facets of the obtained d-Cu O-NF can 2 be identified by a conjunction of the angle between the facets, containing 6 {100} facets and 12 {110} facets. Based on the aforementioned results and TEM/SEM observations, the equilibrium crystal morphology was determined through Wulff construction analysis, which was performed using the VESTA software package to accurately represent the surface energy-dependent faceting behavior.1,2,16-18. 17

Table (Page 17, #1):

BasedontheaforementionedresultsandTEM/SEMobservations,theequilibrium
crystalmorphologywasdeterminedthroughWulffconstructionanalysis,whichwasperformed
usingtheVESTAsoftwarepackagetoaccuratelyrepresentthesurfaceenergy-dependentfaceting
behavior.1,2,16-18.

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Supplementary Fig. 15 | Catalytic performance of propylene epoxidation with O . Arrhenius 2 plotsofpropyleneepoxidationcatalyzedoverthes-Cu O,s-Cu O-NCands-Cu O-NF. 2 2 2 Supplementary Fig. 16 | Microscopic characterization and catalytic performance of s-Cu O- 2 3.(a)SEM, (b)High-angleannulardark-field,(c)elementalmappingimagesofs-Cu O-3and(d) 2 propyleneconversionandproductselectivityovers-Cu O-3. 2 18

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c|Characterizationandcatalyticperformance.TheSEMandTEMimagesofs-Cu O-NFwith 2 (a)3.0mL,(b)15.0mLand(c,d)9.0mLHCletching.(e)Cl2pXPSspectraofs-Cu O-NFusing 2 different concentration of NH OH·HCl. (f) the influence of the controlled variation of Cl supply 2 for propylene conversion and product selectivity over s-Cu O-NF. Reaction conditions: T = 175 2 oC,C H :O :N =10:5:85vol.%,GHSV=36,000h-1,50.0mgcatalyst. 3 6 2 2 19

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Supplementary Fig. 18 | Catalytic performance of propylene epoxidation with O . Propylene 2 conversion and product selectivity over s-Cu O-NF after different HCl etching times. Reaction 2 conditions:T=175oC,C H :O :N =10:5:85vol.%,GHSV=36,000h-1,50.0mgcatalyst. 3 6 2 2 Supplementary Fig. 19 | Catalytic performance of propylene epoxidation with O . 2 Performance comparisons of various coinage-metal-based catalysts in propylene epoxidation includingPOformationrate,PO selectivityandpropyleneconversion.Thedigitalcharactersfrom 1 to 15 correspond to those in Supplementary Table 2. The area of the circles corresponds to the POformationrate,withlargercircleareasindicatingahigherPOformationrate. 20

Table (Page 20, #1):

Theareaofthecirclescorrespondstothe
POformationrate,withlargercircleareasindicatingahigherPOformationrate

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Supplementary Fig. 20 | Catalytic performance of propylene epoxidation with O . Stability 2 test of the s-Cu O-NF in propylene epoxidation at(a) 150 °C, (b) 175 °C, (c) 200 °C and(d) 250 2 °C. Stability test of the (e) s-Cu O-NC and (f) s-Cu O in propylene epoxidation at 175 °C. 2 2 Reactionconditions:C H :O :N =10:5:85vol.%,GHSV=36,000h-1,50.0mgcatalyst. 3 6 2 2 21

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Supplementary Fig. 21 | Characterizations of spent catalysts. (a) Quasi situ XRD, (b) Cu 2p XPS spectra and (c) TEM image of the spent s-Cu O-NF after the DEP reaction at 200 oC. SEM, 2 TEMandHRTEMimagesofs-Cu O-NFaftertheDEPreactionsat(d)150oCand(e)250oC. 2 Supplementary Fig. 22 | Characterizations of various catalysts. (a) The resistance to charge transferspectraand(b)Ramanpatternofthes-Cu O,s-Cu O-NCands-Cu O-NF. 2 2 2 22

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Supplementary Fig. 23 | Characterizations of various catalysts. The data split graph of O - 2 TPD ofthes-Cu O,s-Cu O-NCands-Cu O-NF. 2 2 2 Supplementary Fig. 24 | Characterizations of various catalysts. The H -TPR graph of the s- 2 Cu O-NCands-Cu O-NF. 2 2 23

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Supplementary Fig. 25 | Reaction mechanism. In situ DRIFTS spectra over s-Cu O-NF at 2 different temperatures were recorded after (a) the mix flow of C H , O and N (10: 5: 85 vol.%) 3 6 2 2 or(b)C H adsorption. 3 6 SupplementaryFig.26|Characterizationsofvariouscatalysts.InsituDRIFTSspectraovers- Cu O-NFat150 °CwererecordedafterthePOadsorption. 2 24

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Supplementary Fig. 27 | Characterizations of various catalysts. In situ DRIFTS analysis after exposing s-Cu O-NF to the flow of C H and mix flow of C H , O and N (10: 5: 85 vol.%) at 2 3 6 3 6 2 2 150°Cand250°C. 25

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3.Supplementary Tables SupplementaryTable1|Physicochemicalpropertiestestofas-preparedCu Onanocatalysts. 2 S a Vb BET Sample (m2 g-1) (cm3g-1) s-Cu O 0.710 0.007 2 s-Cu O-NC 12.330 0.093 2 s-Cu O-NF 30.382 0.114 2 c-Cu O-NF 10.120 0.039 2 o-Cu O-NF 4.323 0.013 2 d-Cu O-NF 2.728 0.025 2 aBETsurfacearea;bt-Plotmicroporevolume. 26

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Supplementary Table 2 | Comparison between s-Cu O-NF and other reported coinage- 2 metal-basedcatalystsforpropyleneepoxidationwithO . 2 Conv. POselect. POformationrate Temp. Flowrate Pressure No. Catalyst Ref. (%) (%) (mmolgcat -1h-1) (oC) (mLmin-1) (MPa) 1 CubicCu O 0.80 10 / 225 50.0 0.1 2 2 OctahedralCu O 0.67 3 / 200 50.0 0.1 2 1 Rhombic 3 0.2 50 0.057 250 50.0 0.1 dodecahedraCu2O 4 Rhombic 0.05 95 0.02 150 50.0 0.1 dodecahedraCl- 2 5 Cu2O 1.0 63 0.5 200 50.0 0.1 6 Cu/SiO 0.25 53 0.014 225 50.0 0.1 19 2 7 Ag /Al O / 85 / 110 / / 20 3 2 3 VCe Cu - 0.5 0.5 8 0.26 33 0.165 250 60.0 0.1 21 NaCl 9 Au/TS-1-KOH 0.88 52 0.19 200 20.0 0.1 22 10 Ag-MoO /ZrO 0.6 58 0.236 350 62.5 0.1 23 3 2 11 c-Cu O-27 0.04 79 0.034 90 50.0 0.1 2 24 12 c-Cu O-27 0.06 82 0.050 110 50.0 0.1 2 27

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13 0.03 ~100 0.08 150 30.0 0.1 This 14 s-Cu O-NF 0.15 84 0.18 175 30.0 0.1 2 work 15 1.25 30 0.83 225 30.0 0.1 28

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SupplementaryTable3|AssignmentofIRbandsobservedintheDRIFTSspectra. Wavenumber (cm–1) Assignment Ref. 2954,2980,3100 methyl symmetrical C−Hvibrations 2,25 2752,2815,2856 C−Hstretching splitbyFermi resonance 26–28 C H molecules adsorbed Cu(I) sites or 1440,1473,1540,2920 3 6 1,24 bridging Cu–Osites 2305,2375 asymmetricstretching vibrationof CO 1,29,30 2 1652 adsorbed C H O 24,31,32 3 4 1578 theformation ofglycolate 33 1385,1560 adsorbed HCOO 24,27,34 1288 CHbending-vibration 1,24,35 1180-1210 C–Ostretching 36,37 29

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SupplementaryTable 4 |DFT calculations. Optimized structure ofoxygen speciesand possible intermediates of epoxidation over Cu O {111},{100}, and{110}surfaces. The orange, grey, red, 2 andgreenandwhiteballsrepresentCu,C,O ,O andHatoms,respectively. lat ads Cu O {111} Cu O {100} Cu O {110} 2 2 2 O * 2 E=-1.59 eV E=-0.51 eV E= -0.57eV R(O-O)=1.329Å R(O-O)= 1.234Å R(O-O)= 1.273Å R(O-Cu)= 1.863Å R(O-Cu)= 2.932Å R(O-Cu)= 2.109Å INT-1 E=-1.63 eV E=-0.39 eV E= -0.74eV R(O-Cu)= 1.806Å R(O-Cu)= 1.854Å R(O-Cu)= 1.921Å R(C-Cu)=2.053Å R(C-Cu)= 2.150Å R(C-Cu)= 2.027Å INT-2 E=-2.89 eV E=-2.34 eV E= -1.60eV 30

Table (Page 30, #1):

Theorange,grey,red,

Table (Page 30, #2):

| and | green | and | white | balls | represent | Cu, | C, | O | , lat | O | ads | and | H | atoms, | respectively. | | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- | --- |

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R(O-Cu)= 1.740Å R(O-Cu)= 1.927Å R(O-Cu)= 1.908Å R(C-O )= R(C-O )=1.470Å R(C-O )=1.488Å surf surf surf 1.470Å O* E=-2.75 eV E=-1.46 eV E= -1.92eV R(O-Cu)= 1.782Å R(O-Cu)= 1.760Å R(O-Cu)= 1.894Å 31

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Table (Page 33, #1):

16.K.MommaandF.Izumi.VESTA3forthree-dimensionalvisualizationofcrystal,

Table (Page 33, #2):

volumetricandmorphologydata.J.Appl.Crystallogr.44,1272–1276(2011).

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