Supporting Informtion Ultrfst nd Stble CO Cpture Using Alkli Metl Slt-Promoted MgO-CCO 3 Sorbents Hongjie Cui, Qiming Zhng, Yunwu Hu, Chong Peng, Xingchen Fng, Zhenmin Cheng, Vldimir V. Glvit nd Zhiming Zhou, * Stte Key Lbortory of Chemicl Engineering, Est Chin University of Science nd Technology, Shnghi 0037, Chin. Dlin Reserch Institute of Petroleum nd Petrochemicls, SINOPEC, Dlin 0, Chin. Lbortory for Chemicl Technology, Ghent University, Technologieprk 9, B-90 Gent, Belgium. *Corresponding uthor: zmzhou@ecust.edu.cn S-
. Supplementry Text The texturl properties such s pore size distribution, BET surfce re of supports nd sorbents were determined from N dsorption isotherms t -9 C (Micromeritics ASAP 00). The pore volume nd verged pore dimeter were determined from the dsorption brnch using the Brrett- Joyner-Hlend (BJH) method. The micromorphology of supports nd sorbents ws nlyzed by field emission scnning electron microscopy (FESEM, Nov NnoSEM 0) nd high-resolution trnsmission electron microscopy (HRTEM, JEOL JEM-00) equipped with n energy dispersive spectrometer (EDS, EDAX Genesis XM system). The crystlline structure of the sorbent ws identified by X-ry diffrction (XRD, Bruker D8 Advnce) in the rnge of θ = 0-80 using Cu Kα rdition (λ = 0.8 nm) t room temperture. The in situ XRD study on the CO sorption on the sorbents nd the reverse desorption process ws performed on the Bruker D8 Advnce diffrctometer equipped with high-temperture ttchment (Anton Pr XRK 900). In order to rpidly collect sufficient counts, three seprte scns for θ = 30-3, 3-0 nd 0- were recorded with scn step of 0.0 nd step time of 0.3 s. Thus, it took 7 s to obtin n XRD pttern with θ vlues rnging from 30 to by combintion of the three scns. In typicl procedure, the temperture ws first incresed from room temperture to 30 C t heting rte of 0 C/min under N (0 ml/min), fter which N ws switched to CO (0 ml min - ) for sorption nd t the sme time, XRD scns of durtion min (7 s for scnning nd s between ech scn) were registered in the θ rnge of 30-3. After 0 min of CO sorption t 30 C, CO ws switched bck to N for desorption nd the temperture ws incresed t rte of 0 C min - to 00 C nd kept for 0 min. The diffrction ptterns in the θ rnge of 30-3 were collected t 30, 370, 380, 390 nd 00 C, respectively. By repeting the bove procedure but with different θ rnges (3-0 nd 0- ), the corresponding diffrction ptterns were cquired. In ddition, nother in situ XRD experiment ws crried out, in which the temperture ws incresed from room temperture to 00 C t heting rte of 0 C min - under N (0 ml min - ) S-
while the diffrctogrms were collected ech 0 C t constnt temperture in the θ rnge of 0-80 with scn step of 0.0 nd step time of 0.3 s. S-3
. Supporting Tbles Tble S. Texturl Properties of the MgO-bsed Supports Support MgO content [mol% / wt%] CCO 3 content [mol% / wt%] BET surfce re [m g - ] Pore volume b [cm 3 g - ] Averge pore dimeter b [nm] Mg 00 00 / 00 8.7 0..3 Mg 98 C 98 / 9. /.9 9.7 0.37. Mg 9 9 / 88. /. 8.9 0.3 3. Mg 90 C 0 90 / 78.3 0 /.7.3 0.8 3. Mg(B) 00 00 / 00.8 0.7 9. Mg(B) 9 9 / 88. /. 3. 0.3 7.7 Referring to the nominl content, but indeed lso representing the ctul content becuse no opertions tht my result in the loss of species were performed during the preprtion process. b Determined from the dsorption brnch using the Brrett-Joyner-Hlend (BJH) method. Tble S. Estimted Kinetic Prmeters for AMS-Mg 00 nd AMS-Mg 9 Sorbent T [ C] k [min - ] k [min - ] R 0 0.0 0.0 0.99 AMS-Mg 00 80 0.8 0.0 0.987 300 0. 0.039 0.97 30 0.7 0.0 0.97 0 0.9 0.0 0.999 AMS-Mg 9 80 0. 0.03 0.990 300 0.99 0.0 0.989 30 0.78 0.09 0.99 S-
3. Supporting Figures Volume dsorbed (cm 3 g - ) 00 30 300 0 00 0 00 0 Mg 00 Mg 98 C Mg 9 Mg 90 C 0 dv/dd (cm 3 (gnm) - ) 0.030 0.0 0.00 0.0 0.00 0.00 b Mg 00 Mg 98 C Mg 9 Mg 90 C 0 0 0.0 0. 0. 0. 0.8.0 Reltive pressure 0.000 0 00 Pore dimeter (nm) Figure S. () N dsorption-desorption isotherms nd (b) pore-size distribution (PSD) curves of MgO (Mg 00 ) nd MgO-CCO 3 (Mg 98 C, Mg 9 nd Mg 90 C 0 ), showing unimodl PSD for MgO nd bimodl PSD for CCO 3 -dopnt MgO. The PSD ws determined from the dsorption brnch using the Brrett-Joyner-Hlend (BJH) method. Volume dsorbed (cm 3 g - ) 0 00 0 00 0 AMS-Mg 00 AMS-Mg 98 C AMS-Mg 9 AMS-Mg 90 C 0 dv/dd (cm 3 (gnm) - ) 0.0 0.0 0.00 0.008 0.00 0.00 0.00 b AMS-Mg 00 AMS-Mg 98 C AMS-Mg 9 AMS-Mg 90 C 0 0 0.0 0. 0. 0. 0.8.0 Reltive pressure 0.000 0 00 Pore dimeter (nm) Figure S. () N dsorption-desorption isotherms nd (b) pore-size distribution curves of different AMS-MgO sorbents, showing unimodl PSD for AMS-MgO nd bimodl PSD for CCO 3 -dopnt AMS-MgO. The PSD ws determined from the dsorption brnch using the Brrett-Joyner-Hlend (BJH) method. S-
, -MgO; -MgCO 3 3-N Mg(CO 3 ) ; -K Mg(CO 3 ) 3 00 C min 00 C min 00 C 390 C 380 C 370 C 30 C 30 C 30 3 0 θ (degree), b -MgO; -MgCO 3 3-N Mg(CO 3 ) ; -K Mg(CO 3 ) -CMg(CO 3 ) ; -CCO 3, 3, 00 C 8min 00 C min 00 C min 00 C min 00 C 390 C 380 C 370 C 30 C 30 C 30 3 0 θ (degree) Figure S3. Diffrctogrms recorded by in-situ XRD nlysis during regenertion of () AMS-Mg 00 nd (b) AMS-Mg 9 from 30 to 00 C in pure N. S-
, 33 3 -MgO; -N CO 3 ; 3-K CO 3 ; -KNO 3 0 30 0 0 0 70 80 θ (degree) 00 C 0 C 00 C 30 C 300 C 0 C 00 C 0 C 00 C.0. 3.0 3. θ (degree) 00 o C 00 o C 300 o C 00 o C 00 o C b,, 33 3 -MgO; -N CO 3 ; 3-K CO 3 ; -KNO 3 ; -CCO 3 0 30 0 0 0 70 80 θ (degree) 00 C 0 C 00 C 30 C 300 C 0 C 00 C 0 C 00 C 00 o C 00 o C 300 o C 00 o C 00 o C.0. 3.0 3. θ (degree) Figure S. Diffrctogrms recorded by in-situ XRD nlysis of () AMS-Mg 00 nd (b) AMS-Mg 9 when heting from 00 to 00 C in pure N. There exists slight shift of the MgO (00) pek to lower ngles with incresing the temperture, i.e., bout 0. for AMS-Mg 00 nd 0. for AMS-Mg 00, indicting the lttice expnsion tht origintes from the prtil dissolution of MgO in the molten AMS. S-7
00 Weight percentge (wt%) 80 0 0 0 µm 30 o C 0 0 00 00 300 00 00 00 700 800 Temperture ( o C) Figure S. Thermogrvimetric nlysis of AMS (with composition the sme s tht used for the sorbents) in N (inset: FESEM imge of AMS fter clcintion t 30 C in N, displying smooth surfce). This Figure indictes tht the initil decomposition temperture of AMS is bout 30 C, i.e., the AMS is stble t the tempertures used in this study ( 00 C). 0.8 0.8 b CO uptke (g CO g sorbent - ) 0. 0. 0. 7 o C 300 o C 3 o C 30 o C 37 o C CO uptke (g CO g sorbent - ) 0. 0. 0. 7 o C 300 o C 3 o C 30 o C 37 o C 0.0 0 0 0 30 0 0 0 0.0 0 0 0 30 0 0 0 Time / min Time / min Figure S. CO uptke of () AMS-Mg 00 nd (b) AMS-Mg 9 t temperture rnging from 7 to 37 C under pure CO, indicting tht the optiml sorption temperture of AMS-Mg 00 is 3 C, which is lower thn tht of AMS-Mg 9 (30 C). S-8
0 AMS-Mg 9 E, =.8 kj/mol - AMS-Mg 00 E, =.9 kj/mol ln(k) - AMS-Mg 9-3 AMS-Mg 00 E, =.9 kj/mol - E, =.8 kj/mol -.x0-3.7x0-3.7x0-3.8x0-3.8x0-3.9x0-3 /T (K - ) Figure S7. Activtion energies (E, nd E, ) corresponding to k nd k using the Arrhenius eqution for AMS- Mg 00 nd AMS-Mg 9..0 AMS-Mg 00 CO uptke (g CO g sorbent - ) 0.8 0. 0. 0. 0.0 AMS-Mg 98 C AMS-Mg 9 AMS-Mg 90 C 0 70 o C 00 00 300 00 00 00 Temperture ( o C) Figure S8. Sorption behviors of AMS-promoted MgO-bsed sorbents by temperture rmping t C min - from 00 to 00 C in pure CO. It shows tht the strting desorption temperture in CO for sturted sorbents is bout 70 C, bsed on which the desorption temperture used in this study under the severe condition is set t 00 C. S-9
() fresh sorbents 3,3 - MgO; - CCO 3 3- N CO 3 ; - K CO 3 - KNO 3 Intensity (.u.) AMS-Mg(B) 9 (b) used sorbents, AMS-Mg(B) 80 C 0 - MgCO 3 ; 7- CMg(CO 3 ) 8- N Mg(CO 3 ) ; 9- K Mg(CO 3 ) 7 8 7 7 9 AMS-Mg(B) 9 7 7 AMS-Mg(B) C 80 0 0 0 30 0 0 0 70 80 θ (degree) Figure S9. XRD ptterns of AMS-Mg(B) 9 nd AMS-Mg(B) 80 C 0 : () fresh sorbents nd (b) fter sorption in pure CO t 30 C for min. Volume dsorbed (cm 3 g - ) 00 0 0 80 0 Mg(B) 00 Mg(B) 9 AMS-Mg(B) 9 dv/dd (cm 3 (gnm) - ) 0.030 0.0 0.00 0.0 0.00 0.00 b Mg(B) 00 Mg(B) 9 AMS-Mg(B) 9 0 0.0 0. 0. 0. 0.8.0 Reltive pressure 0.000 0 00 Pore dimeter (nm) Figure S0. () N dsorption-desorption isotherms nd (b) pore-size distribution (PSD) curves of Mg(B) 00, Mg(B) 9 nd AMS- Mg(B) 9, showing unimodl PSD of support nd sorbent prepred by simple method with bsic mgnesium crbonte s the MgO precursor. The PSD ws determined from the dsorption brnch using the Brrett-Joyner-Hlend (BJH) method. S-0
CO uptke (g CO g sorbent - ) 0.8 0. 0. 0. 0.0 b AMS-Mg(B) 9 AMS-Mg(B) 80 C 0 0 00 800 00 0 0 30 0 0 Time (min) c fresh d fter 0 cycles µm µm Figure S. CO uptke profiles of AMS-Mg(B) 80 C 0 : () over 0 cycles under severe condition nd (b) comprison with AMS-Mg(B) 9 t the first cycle. FESEM imges of (c) fresh AMS-Mg(B) 80 C 0 nd (d) 0- cycle used AMS-Mg(B) 80 C 0 under severe condition. S-