Supporting Information

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1 Supporting Information Interrupted Chalcogenide-Based Zeolite-Analog Semiconductor: Atomically Precise Doping for Tunable Electro-/Photoelectrochemical Properties** Jian Lin, Youzhen Dong, Qian Zhang, Dandan Hu, Na Li, Le Wang,* Yang Liu,* and Tao Wu* anie_ _sm_miscellaneous_information.pdf

2 General Methods: Chemicals: Indium powder (In, 99.99%, 200 mesh), selenium powder (Se, 99.95%), bismuth nitrate (Bi(NO 3 ) 3 5H 2 O, 99.99%), and piperidine (PR, 99%) were purchased from Aladdin Industrial, Inc. All chemicals were used as received without further purification. Synthesis of CSZ-5-InSe: Dark orange red single crystals of CSZ-5-InSe were obtained from solvothermal reaction of selenium powder (250 mg, mmol) with indium metal (80 mg, mmol) in the mixed solvents of piperidine (PR, 2.5 ml) and deionized water (1.0 ml) at 170 o C for 7 days. Bismuth doped crystals (denoted as CSZ-5-InBiSe) were synthesized by adding 80 mg bismuth nitrate in the typical reaction procedure of CSZ-5-InSe. Optical Absorption Measurement: Room-temperature solid-state UV-Vis diffusion reflectance spectra of crystal samples were measured on a SHIMADZU UV-3600 UV-Vis-NIR spectrophotometer, by using BaSO 4 powder as the reflectance reference. The absorption spectra were calculated from reflectance spectra by using the Kubelka-Munk function: F(R)=α/S=(1-R) 2 /2R, where R, α, and S are the reflection, the absorption and the scattering coefficient, respectively. In order to determine band edge of the direct-gap semiconductor, the relation between the absorption coefficients (α) and the incident photon energy (hυ) is exhibited as αhυ= A(hυ E g ) 1/2, where A is a constant that relates to the effective masses associated with the valence and conduction bands, and E g is the optical transition gap of the solid material. The band gap of the obtained samples can be determined from the Tauc plot with [F(R)*hυ] 2 vs. hυ by extrapolating the linear region to the abscissa. Structure Characterization: Single crystal X-ray diffraction (SCXRD) data were performed on Agilent diffractometers at low temperature (223K) with graphite monchromated Mo Kα (λ = Å) radiation. The structures were solved by direct methods using SHELXS-97 and the refinements against all reflections of the compounds were performed using SHELXL-97. The protonated piperidine cations located in the channel of anion framework were also refined with routine constraint instructions. Relevant crystal data, collection parameters, and refinement results can be found in Table S1. The net of CSZ-5-InSe was computed using TOPOS software. The visualization of net and tiling was generated using 3dt. Powder X-ray diffraction (PXRD) data were collected on a desktop diffractometer (D2 PHASER, Bruker, Germany) using Cu-K α (λ= Å) radiation operated at 30 kv and 10 ma. Variable temperature powder X-ray diffraction (PXRD) data were collected on a diffractometer (D8 S1

3 ADVANCE, Bruker, German) equipped with high temperature in situ vacuum reaction attachment at a heating rate of 5 o C min -1. Structural refinement indicates that the atomic temperature factor of terminal atom bonded to specific indium site X in the cluster B is greatly different from that of other Se sites. If it is identified as Se atom, its atomic temperature factor is abnormally much larger than that of other Se atoms. When identified as O atom, its atomic temperature factor becomes more reasonable. Obviously, O atom is from water molecules by taking consideration of bond length of In-O and charge balance between anionic framework and template cations. Crystallographic data for CSZ-5-InSe: In 28 Se 54 (H 2 O) 4 24(H-PR) 4(H 2 O), M r = , cubic, F-43c, a= (3)å, V= (8)Å 3, Z=8. 2θ max =49.96, ρ calcd =2.257gcm -3, µ=9.143mm -1, total reflections, 2754 observed (I>2σ(I)), R 1 =0.0534, wr 2 =0.1293, GOF = Crystallographic data for CSZ-5-InBiSe: In 26 Bi 2 Se 54 (H 2 O) 2 24(H-PR) 4(H 2 O), M r = , cubic, F-43c, a= (7)å, V= (2)Å 3, Z= 8. 2θ max =49.94, ρ calcd =2.267gcm -3, µ= mm -1, 6743 total reflections, 1870 observed (I>2σ(I)), R 1 =0.0738, wr 2 =0.1749, GOF= CCDC and contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via Thermogravimetric (TG) Measurement: Thermogravimetric analysis was performed on a Shimadzu TGA-50 thermal analyzer by heating each sample from room temperature to 800 o C with ramping rate of 5 o C/min under nitrogen flow. Temperature Programmed Desorption-Mass (TPD-MS) Measurement: Temperature programmed desorption-mass spectroscopy (TPD-MS) was tested on a ChemBET pulsar TPR/TPD automated chemisorption analyzer (Quantachrome instruments) equipped with a mass spectrometer. Testing sample was heated from 20 o C to 400 o C with ramping rate of 5 o C/min under helium flow. Before testing, the system was purged with helium gas for two hours to stabilize the background signals (H 2 O and trace of impurity gas CO 2 and N 2 mixed in the carrier gas). Element Analysis: Elemental analysis of C, H, and N are performed using a VARIDEL III elemental analyzer. Energy dispersive spectroscopy (EDS) analysis was performed on scanning electron microscope (SEM) equipped with energy dispersive spectroscopy (EDS) detector. Data acquisition was performed at an accelerating voltage of 25 kv and 40s accumulation time. S2

4 XPS Measurement: X-ray photoelectron spectroscopy (XPS) data were collected with a Leeman prodigy spectrometer equipped with a monochromatic Al Kα X-ray source and a concentric hemispherical analyzer. Photoelectrochemical Measurement: To prepare the electrode for photo-electrochemical measurements, 2 mg of the CSZ-5s crystals were first ground into fine powders using a marble and pestle, and then added into 200 µl of 0.5% nafion (ethanol). The mixture was then subjected to sonication in a water bath until the sample was homogeneously dispersed in the nafion solution. The ITO slices were sonicated in acetone, NaOH (1M) in 1:1 (v/v) ethanol/water, and water, respectively, for about 15 min of each run. Before coated with samples, the ITO substrates were cleaned with UV-ozone plasma for at least 15 minutes to remove the organic residues. After that, 100µL of the compound suspensions were dropped onto the surface of ITO substrate, which were masked by a 3M scotch tape with surface area of 0.75 cm 2 and then dried at room temperature. This step was repeated for twice to obtain a uniform coverage of the samples on ITO. (A) Mott-Schottky Curve: The Mott-Schottky plots of the CSZ-5s were generated using PARSTAT 2273 (Princeton Applied Research Solartron Analytical, Advanced Measurement Technology, Inc). The capacitance of the semiconductor-electrolyte interface was collected at 1 khz, with 10 mv AC voltage amplitude, in the same electrolyte (0.5 M Na 2 SO 4 ) and setup for PEC measurements. (B) Photocurrent-Voltage (J-V) Behavior: The photoelectrochemical tests were performed in a 30 ml extrasil quartz cell filled with 0.5M Na 2 SO 4 aqueous solution, using an electrochemical workstation (CHI 1030b). Prior to the measurement, the electrolyte was deaerated by purging with nitrogen continuously for 30 minutes. A 300 W xenon lamp used as the standard light source, and the illumination intensity on the surface of the photoelectrode was ~170mW/cm 2.Three-electrode set-up with a platinum electrode and a silver-silver chloride electrode (Ag/AgCl, in 3 M KCl) as the counter and reference electrodes was used to study the photocurrent responses and linear sweep voltammetry. Electrochemical Measurement: All experiments were performed at room temperature. Before each measurement, the glassy carbon electrode (GCE) surface was polished by using 50 nm Al 2 O 3 slurry and washed with ethanol and deionized water in ultrasonic bath. The electrochemical cell was assembled with a conventional three-electrode system: a glassy carbon working electrode, an Ag AgCl/KCl (saturated) reference electrode, and a Pt wire counter electrode. The homogeneous inks were prepared by dispersing 1 mg commercial In 2 Se 3 or as-prepared CSZ-5s and 19 mg carbon black in 20 ml water solution with at least 30 S3

5 min sonication, which were labelled as In 2 Se 3 /CB and CSZ-5s/CB. Then 6 and 20 ml of the catalyst inks were coated onto a clean GCE of 3 mm and 5 mm in diameter for CV and RDE measurements, respectively. Electrochemical measurements were performed using a CHI 830 electrochemical analyzer coupled with a RDE system (Princeton Applied Research, Model 616). S4

6 Figure S1. (a) TG curve in the N 2 gas flow. (b) Variable temperature powder X-ray diffraction patterns of CSZ-5-InSe. (c) Variable temperature powder X-ray diffraction patterns of CSZ-5-InBiSe. [Both CSZ-5-InSe and CSZ-5-InBiSe can be stable up to 180 o C. The crystal lattice water molecules in the channel are easy to escape from pores or channels below 200 o C, and no crystal collapse is observed. However, the weakly bonded H 2 O molecules at the corner of cluster B are released out of framework when above 200 o C. This is because water removal gives rise to an extremely unstable In 3+ with pyramidal coordination geometry, which causes collapse of the framework of CSZ-5-InSe beginning at around 200 o C. Thus far, it is unfortunate that no porosity is available when degassed at mild temperature under vacuum.] S5

7 Figure S2A. (a) Signals of CO 2, N 2, O 2, H 2 O (6.43*10-8 Torr) and OH - before gas purge. (b) Signals of CO 2, N 2, O 2, H 2 O (1.23*10-8 Torr) and OH - after purge with helium gas for two hours. (c) Signals of CO 2, N 2, O 2, H 2 O (1.55*10-8 Torr) and OH - after heating for 15 minutes, corresponding to around 70 o C, and the water signal intensity increases gradually. (d) Signals of CO 2, N 2, O 2, H 2 O (1.58*10-8 Torr) and OH - after heating for 20 minutes, corresponding to around 95 o C, and the water signal intensity increases gradually. (e) Signals of CO 2, N 2, O 2, H 2 O (1.36*10-8 Torr) and OH - after heating for 30 minutes, corresponding to around 145 o C, and the water signal intensity decreases gradually. (f) Signals of CO 2, N 2, O 2, H 2 O (1.44*10-8 Torr) and OH - after heating for 40 minutes, corresponding to around 195 o C, and the water signal intensity increases again. S6

8 Figure S2B. (g) Signals of CO 2, N 2, O 2, H 2 O (2.27*10-8 Torr) and OH - after heating of 42 minutes, corresponding to around 205 o C, and the water signal intensity increases again accompanied with appearance of other signals. (h) Signals of CO 2, N 2, O 2, H 2 O (3.05*10-8 Torr) and OH - after heating for 47 minutes, corresponding to around 230 o C, and the intensity of both water signal and other signals increase significantly. (i) Signals of CO 2, N 2, O 2, H 2 O (2.51*10-8 Torr) and OH - after heating for 55 minutes, corresponding to around 270 o C, the signal intensity for all discomposed species decreases gradually. (j) Signals of CO 2, N 2, O 2, H 2 O (2.51*10-8 Torr) and OH - after heating for 75 minutes, corresponding to around 370 o C, and the signal intensity for all discomposed species decreases greatly. S7

9 Figure S3. (a) Illustration of temperature rising and heat flux signal variation at different time stage. (b) TPD-MS pattern of H 2 O and OH - at different time stage. (c) TPD-MS pattern of CO 2 at different time stage. (d) TPD-MS pattern of N 2 and C 2 H 4 at different time stage. [One clear broad signal peak is observed for both H 2 O and OH - species during time range of 120 to 150 min, which is attributed to desorption of physical adsorbed water in the pores of CSZ-5-InSe. The other dual peaks for both H 2 O and OH - species appear during time range of 160 to 190 min, which is ascribed to desorption of chemically bonded coordination water and the thermal decomposition of piperidine in the CSZ-5-InSe.] S8

10 Figure S4. Crystallographically asymmetric unit in the framework of CSZ-5-InSe. Figure S5. Left: the cluster A connected to four cluster B; Right: cluster B connected to three cluster A and terminated by water molecule. S9

11 Figure S6. Schematic illustration of structure simplification. (a) Cluster A represents 4-connected node and cluster B acts as 3-connected node in the simplified structure. (b) Adamantane cage α is composed of six cluster A and four cluster B, cage β is formed by twelve cluster A and sixteen cluster B. (c) Cage β is surround with eight cage α. (d) Four adamantane cage α are fused to form a cage β by missing centrally shared cluster. (e) Two kind of cages orderly arranged in (3, 4)-connected boracites topology. Figure S7. Left: 3D interconnected channel system in the framework of CSZ-5-InSe; Right: illustration of the channel system in bor-a net by natural tiling. S10

12 Figure S8. Derivative relationship of three topological networks of bor, bor-a, and qzh. The ratio of the number of 3-connected vertex vs. that of 4-connected vertex for each net is listed in bracket. Figure S9. SEM image and EDS analysis of the crystal of CSZ-5-InBiSe. S11

13 Figure S10. Bi 4f XPS spectrum of CSZ-5-InBiSe. Figure S11. Mott-Schottky plot of In 2 Se 3 measured at a frequency of 1k Hz. S12

14 Figure S12. (a) Cyclic voltammograms of In 2 Se 3 /CB, CSZ-5-InSe/CB, CSZ-5-InBiSe/CB and UCR-2-InSe/CB in O 2 -saturated 0.1 M KOH solutions. Scan rate: 50 mv s -1. (b) RDE voltammograms at different rotation rates of UCR-2-InSe/CB. (c) The corresponding Koutecky-Levich plots at different potentials of UCR-2-InSe/CB. (d) 3D framework of open-framework UCR-2-InSe viewed along c axis. S13

15 Table S1. Crystal data, parameters and refinement results of CSZ-5-InSe and CSZ-5-InBiSe. CSZ-5-InSe CSZ-5-InBiSe Empirical formula a In 28 Se 54 (H 2 O) 4 24(H + -PR) 4(H 2 O) In 26 Bi 2 Se 54 (H 2 O) 2 24(H-PR) 4(H 2 O) Formula weight a Crystal system cubic cubic Z 8 8 Space group F-43c (No.219) F-43c (No.219) a=b=c(å) (3) (7) α=β=γ(deg.) V (Å 3 ) (8) (18) F(000) D c (g cm -3 ) µ (mm -1 ) Crystal morphology Bulk Cubic 2θ max (deg.) Collected reflections Independent reflections 3523 (R int = ) 3052(R int = ) Observed reflections Parameters/restrain/data 177/108/ /108/1870 GOF on F R 1, wr 2 (I>2σ(I)) b , , R 1, wr 2 (all data) , , Diff peak, hole (e Å -3 ) 1.167, , a according to refinement result. b R 1 = F o - F c / F o, wr 2 = [ w(f o 2 -F c 2 ) 2 / w (F o 2 ) 2 ] 1/2 S14

16 Table S2. C, H, and N elemental analysis of CSZ-5-InSe and CSZ-5-InBiSe. CSZ-5-InSe C wt% N wt% H wt% C at% N at% C/N ratio Batch Batch Average CSZ-5-InBiSe C wt% N wt% H wt% C at% N at% C/N ratio Batch Batch Average [The average of C/N ratio in for CSZ-5-InSe and CSZ-5-InBiSe is around 4.85, which is close to the ideal ratio in the PR (C/N = 5). The total weight percentage of C, H, and N in the CSZ-5-InSe is wt%, which is also close to the calculated value (21.59 wt%) from the composition of In 28 Se 54 C 120 H 298 N 24 O 4 in the CSZ-5-InSe.] S15

17 Table S3. Topological information on bor, bor-a, and qzh net. Number of the Number of the Ratio of number Net type of 3-Connected type of 4-Connected of 3-C vertex vs number of 4-C Vertex symbol a vertex vertex vertex bor 1 1 4:3 (6.6.6)( ) bor-a 1 1 1:1 ( )( ) qzh 1 2 1:6 ( *)( )(3.3.3) a Size and number of the shortest ring on each angle of the T-atom (M. O'Keeffe and S.T. Hyde, Zeolites1997, 19, 370); * = no closed ring at this angle. Table S4.Topologically related information on three types of vertexes in qzh net. Vertex C.N. x y z Symbolic Wyckoff Symmetry Order T x, x, z 12 i m 2 T x, x, z 12 i m 2 T x, x, 1-x 4 e 3m 6 Vertex CS 1 CS 2 CS 3 CS 4 CS 5 CS 6 CS 7 CS 8 CS 9 CS 10 Cum 10 Vertex Symbol T * T T S16

18 Table S5.Band position of CSZ-5-InSe and CSZ-5-InBiSe by DRS and Mott-Schottky plot. E fb E fb a E CB b E VB c E CB d E VB e Materials E BG (ev) (V, vs. Ag/AgCl) (V, vs. NHE) (V, vs. NHE) (V, vs. NHE) (ev, vs. Vacuum Level) (ev, vs. Vacuum Level) In 2 Se CSZ-5-InSe CSZ-5-InBiSe a E fb (V, vs. NHE) = E fb (V, vs. Ag/AgCl) V b E CB (V, vs. NHE) = E fb (V, vs. NHE) - 0.1V c E VB (V, vs. NHE) = E BG - [- E CB (V, vs. NHE)] d E CB (ev, vs. Vacuum Level) = - E CB (V, vs. NHE) (at 298K) e E VB (ev, vs. Vacuum Level) = - E VB (V, vs. NHE) (at 298K) S17

19 Table S6. The fitting data for corresponding Koutecky-Levich plots at different potentials of CSZ-5-InSe/CB electrode. Potential (V) Slope Intercept n J k Notes: The electron transfer number (n) and kinetic limiting current density (J k ) involved in ORR at each electrode was analyzed by RDE and calculated on the basis of the K- L equations given below [Eqs. (1) - (3)]: 1 J = 1 J K + 1 J L = 1 Bω 1/2 + 1 J K (1) B = 0.62nFC 0 D 0 2/3 ν -1/6 (2) J K = nfkc 0 (3) where J is the measured current density, J K and J L are the kinetic and diffusion limiting current densities, ω is the electrode rotating rate (ω = 2πN, N is the linear rotation speed), n is the overall number of electrons transferred in the oxygen reduction, F is the Faraday constant (96485 C mol -1 ), C 0 is the bulk concentration of O 2, D 0 is the diffusion coefficient of O 2 in the KOH electrolyte, ν is the kinetic viscosity of the electrolyte, and k is the electron transfer rate constant. S18

20 Table S7. The fitting data for corresponding Koutecky-Levich plots at different potentials of UCR-2-InSe/CB electrode. Potential (V) Slope Intercept n J k S19