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Contents

1 2 3 4 Introduction Motivation Objectives Model and Methodology 4.1 Vertex displacement . . . . . . . . . . 4.1.1 Metropolis acceptance criteria 4.2 Tetrahedral displacement . . . . . . . 4.3 Tetrahedral rotation (Random) . . . . 4.4 Tetrahedral rotation (Directional) . . . 4.5 Cluster displacement . . . . . . . . . 4.6 Cluster rotation . . . . . . . . . . . . 4.7 Reaction . . . . . . . . . . . . . . . . 4.8 Simulation details . . . . . . . . . . . Results and Discussion Future plans 1 2 3 4 5 5 6 6 8 8 8 8 11 11 17

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Introduction

We are witnessing some of hottest days of this millennium and this increase in global temperature, termed global warming, has caused various climate changes, such as rise in sea level, change in precipitation pattern, increase in frequency of heat shock, hurricane, oods, etc. 1 Global warming is mainly caused by increase in emission of green house gases (GHGs) (such as water vapour, carbon dioxide (CO2 ), methane, chlorouorocarbon, nitrogen oxides etc). From 1970 onwards there has been an increase of 70% in GHGs, since 1970. Among them, amongst them, 77% is contributed by CO2 . The CO2 release is majorly due to human activities and major sources of emission are, energy (25.9%), industry (19.4%) and transport sectors (13.1%). 2 In order to pacify the adverse eects of climate change, CO2 emission has to be attenuated. The treatment of CO2 involves capture of CO2 from ue stream, transportation of CO2 and storing it in isolation. At current technology treatment for CO2 costs 51 330 US $ per tonnes of CO2 . 2 To mitigate eect of CO2 , it is estimated that, by 2030, 5.6 giga tonnes of CO2 per year should be treated at a cost < 100 US$ per tonnes of CO2 . 1 Techniques available for removal of CO2 are, absorption in suitable solvent, conversion into metal carbonate and adsorption on suitable porous medium. Most widely used technology for CO2 removal is absorption of CO2 in organic solvent like monoethanolamine (MEA), however, organic solvents are hazardous and expensive to use.The CO2 can be converted into solid inorganic carbonate by treating with metal oxides such as MgO, CaO, which avoid usage of organic solvents, however, this technique have high energy requirement 1.62.8 times of current requirement). The CO2 could be adsorbed over suitable porous adsorbent. Adsorbent with large surface area, high pore volume and high anity to CO2 is preferred. Activated carbon which is commonly used as adsorbent in chemical industry has adsorption capacity of 48.4-52.8 mg of CO2 per g of adsorbent. 3 The adsorption capacity decreases in presence of water and regeneration of adsorbent is dicult. Zeolites, which are mesoporous material of alumina and silica, have adsorption capacity of 53 mg of CO2 per g of adsorbent with good regeneration capacities. The adsorption capacity of zeolites has poor dependency on pressure at high pressure region (from 2 to 20 bars) although, it has signicant increase in capacity at lower pressure region (upto 1.4 bars). 4 Molecular sieves, which separate molecules based on its size, have adsorption capacity of 264-308 mg of CO2 per g of adsorbent, with increase in adsorption at higher pressure. Silica aerogel, which is a mesoporous, material of silica has adsorption capacity of 135 mg of CO2 per g of adsorbent, which decreases in presence of water. Modication of silica aerogel with polyethylenimine (PEI), increases the adsorption 1

capacity up to 245 mg of CO2 per g of adsorbent. 5 This suggest that silica aerogel is potential material in CO2 capture application. In general adsorption capacity of porous material depends on various factors such as pore size, fractional free area and specic surface area. Study in silica system would help to synthesis silica based materials of desired properties. The goal of this project is to utilize silica based product for CO2 capture and hence there is a need to study silica systems. We begin with simple system of silica, which is silica aerogel.

Motivation

Silica aerogel is a coherent aggregate of sub-micron particles of colloidal silica, forming three dimensional network in mesoporous range. Majority of its pores lies in the range of 2-50 nm, as a result has high surface area of 500-12000 m2 /g. 6 Aerogels are low density materials (having density of around 0.003 g/cm3 ), where its interstitial space is occupied by air. 7 Availability of large specic surface area makes it a potential material for catalyst and catalyst support. This was recently demonstrated in synthesis of methanol from carbon monoxide, where silica aerogel was used to support Cu-Zr catalyst. 8 Silica aerogel absorbs radiation in IR region and has extremely low thermal conductivity (<3 W/mK ). Hence, can be used as a promising material for transparent window insulator. 9 Silica aerogel has also been used in trapping high velocity cosmic particle in space. 10 Properties of silica aerogel are due to silica linkage and network at molecular level, which depends on synthesis route, suggesting, heart of expressing the nal properties in aerogels lies in its synthesis protocol. Conventionally silica aerogel is prepared using sol-gel process, which is inuenced by various parameters, such as, concentration of precursor, pH, gelation time etc. 6 Still at molecular level how the structure is evolved is not clearly understood. Such understanding will have signicant impact in controlling structure and designing properties in aerogel. Insight on polymerization pathway are not only limited to silica aerogel alone and can be used to study other porous and ordered mesoporous materials like zeolite. Selective adsorption depends on interaction between guest molecule and host molecules. This interaction largely depends on three dimensional network of adsorbent material, anity towards guest molecules. Choice of molecular arrangement depends on protocol of synthesis, which, can be used to desired orientation at molecular level.

Objectives

The objective of this study are. To, understand the silica system using suitable model. device a protocol to synthesis aerogel of desired properties. enhance aerogels CO2 adsorption capacity. Silica aerogel materials are obtained using condensation and hydrolysis reaction of silica precursor, termed as silica polymerization. In experimental studies, usually, kinetics of polymerization are obtained using nuclear magnetic resonance (NMR) and structural morphology are predicted using small angle x-ray scattering (SAXS). However, experimental techniques are bounded by physical limitation of respective resolution. Further, results are inferred from measurable quantites, which are averaged values. Nevertheless, in principle, employing appropriate models, simulations can evaluate actual system, at multiple length and time scale. Major challenges in modeling silica system are large system sizes and long time required to achieve gelation and developing appropriate interactive potential. 11 Initial approach to simulate silica system was to perform reaction kinetics. However, silicon been capable of forming four bonds, has 15 distinguishable reaction environments and 165 rates constant. 12 Since, all the rate constants are determined using experiments, it is near impossible to isolate each species and obtain all the rate constants. By assuming only ve distinguishable Si species, based on number of bridging oxygen, simulations were performed using bimolecular reaction. Although, such simulation agrees with initial evolution of silica species ( Q0 , Q1 and Q2 ), shows deviation from experimental values at longer time. In attempt, to successfully predict Qn evolution, Monte Carlo moves were performed with lattice restrictions. Lattice restriction connes displacement of atoms to grids, which lowers the degree of freedom. Such simulations are computationally less expensive, however, conveys limited information. To answer such diculty, Feuston and Garofalini 13 studied silica system using molecular dynamics by elevating temperature and concentration to achieve gelation in accessible time scale of few nano seconds. Due to elevation in temperature, their Qn distribution does not agree with experimental distribution. Tetrahedral model using Reaction ensemble Monte Carlo simulation covers most of drawback of aforementioned methodologies. It tries to mimic real system by anticipating possible moves by tetrahedron. In this report we have tried to cover the major aspects to REMC and tried to reproduce the results of previous study 11 .

Model and Methodology

To understand mechanical behaviour of silica at molecular level, silica units can be represented by tetrahedral geometry. 14 Each of the tetrahedral units comprises of hard sphere at center, representing silicon atom and vertex consisting of four point particles representing hydroxyl group (OH) or bridging oxygen (BO). At this moment there is no distinction between OH/BO. Although corners of tetrahedral can be shared by more than one tetrahedron, overlapping of centres is prevented by maintaining hard sphere interaction between two silicon atoms. As represented in Equation 1. Where, r is distance between two silica atoms. , r 0, r

U HS =

(1)

To include bond vibrations in the model, tetrahedron is treated as exible structure by imposing harmonic spring between OH/BO groups. The bond distortion potential U1 is represented by Equation 2. Where, ri is position of OH/BO and r0 is equilibrium distance.
4 3

U1 =
i=1 j=i+1

ks (|ri r j | r0 )2 2

(2)

Reactions occurring in silica polymerization are generalized in Equation 3. S i OH + HO S i S i O S i + H2 O (3)

Where, forward reaction is condensation and backward reaction is hydrolysis. Condensation reaction leads to connection of two tetrahedron via BO. Angle potential U2 , for S i O S i angle is evaluated using harmonic spring potential represented by Equation 4. Where is angle formed between S i O S i bonds and 0 is equilibrium angle. kA (cos cos0 )2 (4) 2 The parameters for hard sphere, corner sharing exible tetrahedral model are obtained from Density functional theory (DFT) studies and are reported in literature. 14 These parameters are tabulated in Table 1. In sampling of silica polymerization there are various events which are required to simulate so that simulation closely mimic the real system. Objective of simulation is to study the evolution of silica structure,in addition, also to understand the U2 = 4

Table 1: Parameters of tetrahedral model Parameter SiSi , (A) kS ,(kJ mol1 A2 ) kA ,(kJ mol1 ) r0 , (A) 0 , (deg) Value 2 851 226.74 2.61 155

pathway to silica polymerization. Hence, modelling of various moves are essential. Such moves are explained in subsequent subsections.

4.1

Vertex displacement

At molecular length scale, every particle is set into the motion, depending on its thermal energy. In addition, there are intra molecular motions which also accounts for system energy. To anticipate the movement of OH/BO, vertex displacement move is invoked. In vertex displacement move, randomly selected vertex (OH/BO) is displaced randomly within predened distance, dr. Displacement of vertex move, incorporates the distortion of tetrahedron. Such distortions, results into, shift of center by forth of the total displacement. Move is initial checked for its hard sphere overlapping with centres of other tetrahedrons. Followed by, bond distortion, U1 and angle distortion, U2 energies. The moved is accepted/rejected as per Metropolis acceptance criteria (see sub section 4.1.1). Detail of algorithm is explained in owchart, Figure 1a.

4.1.1

Metropolis acceptance criteria

Metropolis acceptance criteria is a scheme to accept/reject the move based on probability of two ensemble. Probability of an ensemble is given by equation 5 where Ui is probability of existing of ith ensemble, is Boltzmann parameter and Z is partition function. P(i) = e
U i N

/Z,

Z=
i=1

e U i

(5)

Metropolis scheme enable us to accept/reject the move based on the ratio of two probabilities of two (initial and nal) congurations. To manifest lowering of total 5

system energy, move is accepted for system directing towards low energy. However, move can be accepted, even when, move leads to higher energy. The acceptance of such move depends on probability of conguration to exist. This ensures Boltzmann distribution in an ensemble. Ratio of two probabilities, e(Ui+1 Ui ) , gives Boltzmann factor, which is probability of accepting the move. With an uniform random number (occurrence of numbers between 0 and 1 is equal) Boltzmann factor is compared. If Boltzmann factor is more than Random number then the move is accepted, else, rejected. Higher the dierence in energies (for new conguration with higher energy), less likely it would be occurred. Thus, without obtaining partition function, simply by knowing two energies of dierent conguration, decision of accepting / rejecting the move could be executed. This scheme is know as Metropolis acceptance criteria.

4.2

Tetrahedral displacement

Tetrahedral displacement move anticipate the displacement of entire tetrahedron. In real system every silica unit is moves, depending on how they are bonded with other tetrahedron. In this move, randomly selected tetrahedral unit is displaced within predened distance, dr. The selected tetrahedral can be free or bounded, as in reality, leading to calculation of additional U1 and U2 . Prior to energy dierence, hard sphere interaction is calculated.The nal acceptance of move depends on Metropolis acceptance criteria (see subsection 4.1.1). For each accepted move new energy is updated and for each rejected move initial conguration is restored back. Algorithm is explained in ow chart Figure 1b.

4.3

Tetrahedral rotation (Random)

Many a times, molecules retains its position but changes its orientation, this depends on how a molecule orients with its surrounding molecules / environment. Orientation also facilitates reaction as two reacting group may come closer by rotation moves. With this move, more conguration can be covered for a given ensemble, for a xed number of simulation. In this move entire of tetrahedral is rotated around its center, with maximum of predened angle, d. At this moment axis of rotation passes through the center, although, it is not necessary. In random rotation, the tetrahedral is rotated around any random axis. With every such move, U1 and U2 are evaluated for bonded tetrahedral (for tetrahedral there is no such energies associated). U HS interaction is used to nd overlapping and move is accepted for all not overlapped molecules, as per metropolis acceptance criteria (see subsection 4.1.1). The algorithm for tetrahedral rotation in random direction is illustrated in owchart, Figure 2a. 6

Start

Select a random tetrahedral, p i=1 to 4

Start

No

Is ith O is bridging?

Select a random vertex, p

Yes Find out second tetrahedral attached

Calculate bond distortion energy, U1

j=1 to 4

ji

Calculate U1 between, ith and jth Oxygen

Calculate U1and U2 with other tetrahedral if is p bridging oxygen,


No
Is jth O is bridging?

Uold=U1+U2

Yes

Randomly displace p with dr

Calculate U2 for jth Oxygen

Calculate UHS for center with all Si

Calculate U2 for ith Oxygen

Do centers overlap? No Calculate new U1+U2, Unew

Yes

Uold=U1+U2

Randomly displace tetrahedral with dr

Calculate UHS for center with all Si

Yes

Compare U old and U new Is Metropolis move accepted?

No

Do centers overlap? No Calculate new U1+U2 energy, Unew

Yes Accept the move and update energy

Reject the move and restore old configuration

Is Move accepted as per Metropolis criteria?

No

Yes

End

Accept the move and update energy Reject the move and restore old configuration

(a) Vertex
End

(b) Tetrahedral

Figure 1: Flowchart for displacement moves

4.4

Tetrahedral rotation (Directional)

This is move is similar to above mentioned move, however, has little dierence. In real system, sometimes rotation about S i O bond is more favourable. This will happen when a selected tetrahedral unit is bonded from one vertex and free to rotate along selected bond. Without this move it would have taken many moves of random rotation to get same orientation of tetrahedral. This move can also occur when selected tetrahedron is connected to more than one tetrahedron, this incorporates expenditure of energy, thereby lowering the probability. The move is accepted based on U HS interaction and Metropolis acceptance criteria (see subsection 4.1.1). The detail of algorithm is illustrated in owchart in Figure 2b.

4.5

Cluster displacement

Cluster displacement move mimics the displacement of entire aggregate of silica. The movement of aggregate depends on diusivity of aggregate, which in turns depends on size of aggregate. Larger the size of cluster, more would be its resistance to move and lesser would be extend of its displacement. In this move, cluster of randomly selected tetrahedral is displaced with maximum of predened distance, dr. Only hard sphere overlapping is considered, as there is no distortion in bond nor in angle. Based on overlapping move is accepted or rejected. The detailed description of algorithm is illustrated in owchart, Figure 3.

4.6

Cluster rotation

Cluster rotation move is means to encompass possible orientation of cluster. Clusters may rotate and orient as per their favourable conguration. Simulation of this move involves bond stretching and eventually leads to displacement of center of tetrahedral and angle distortion. Hence, in this move along with U HS ,U1 and U2 are calculated. Hard sphere overlapping and metropolis acceptance criteria are used to accept / reject the move. The detailed description of algorithm is illustrated in owchart, Figure 4.

4.7

Reaction

According to Equation 3 there are two reactions occurring simultaneously in the system. Forward reaction is condensation reaction, involves clubbing of two OH groups. Where as, backward reaction (hydrolysis reaction) involves splitting of BO into two OH group. Thus this move resemble the reactions occurring in real system. In simulation, the probability of occurrence of such moves depends on

Start
Start

Select a random tetrahedral, p i=1 to 4


i=1 to 4

Select a random tetrahedral, p

No

Is ith O is bridging?

No

Is ith O is bridging?

Yes Find out second tetrahedral attached j=1 to 4


j=1 to 4

Yes Find out second tetrahedral attached ji Calculate U1 between, ith and jth Oxygen

ji
th th

Calculate U1 between, i and j Oxygen

No

No

Is jth O is bridging?

Is jth O is bridging?

Yes

Yes

Calculate U2 for jth Oxygen

Calculate U2 for jth Oxygen


Calculate U2for ith Oxygen

Calculate U2 for ith Oxygen


Uold=U1+U2

Uold=U1+U2
Randomly select vertex (1-4) for rotation, v

Translate center to origin, O (0,0,0)


Translate center to origin, O (0,0,0)

Randomly select axis (x,y,z) for rotation, v


Calculate Eulers angle, , , (d)

Rotate randomly along v with d

Rotate the tetrahedral as per Eulers angle

Translate center back to initial position

Translate center back to initial position

Calculate UHS for center with all Si

Calculate UHS for center with all Si

Do centers overlap? No Calculate new U1+U2, Unew

Yes

Do centers overlap? No

Yes

Calculate new U1+U2, Unew

Is Move accepted as per Metropolis criteria?

No

Is Move accepted as per Metropolis criteria?

No

Yes

Yes Accept the move and update energy

Accept the move and update energy

Reject the move and restore old configuration


End

Reject the move and restore old configuration

End

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(b) Directional

(a) Random

Figure 2: Tetrahedral rotation

Start

Select a random tetrahedral, p

Find out all tetrahedral connected in the cluster of p

Calculate U1 and U2, Uold

Start
Calculate center of all Si

Select a random tetrahedral, p


Translate center to origin, O (0,0,0)

Find all tetrahedral connected in the cluster of p

Randomly select axis (x,y,z) for rotation, v

Displace entire cluster with dr

Rotate randomly along v with d

Calculate UHS for all Si in a cluster with all other Si

Translate center back to initial position

Calculate UHS for all Si in cluster with all Si

Do centers overlap? No Accept the move

Yes
Yes Do centers overlap? No Calculate new U1+U2, Unew

Reject the move and restore old configuration

End

Is Move accepted as per Metropolis criteria?

No

Yes

Figure 3: Flowchart for Cluster displacement

Accept the move and update energy

Reject the move and restore old configuration

End

Figure 4: Flowchart for Cluster rotation

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equilibrium rate constant and standard Gibbs energy of reaction. Although polymerization involves multicomponent system, equilibrium rate constant is consider to be same for all reactions. The approximation of Keq = 500 is supported by DFT studies reported in literature 15 . In this move two randomly selected OH groups are replaced by BO. This manifests in increase in reaction rate. To set back to more realistic move, the probability of occurrence of such move is kept very low. Reaction can occur between two OH group of dierent cluster or within same cluster. Inter cluster reaction leads to increase in cluster size whereas, intra cluster reaction leads to sever distortion of cluster. This distortion can be mollied by introducing system relaxation. System relaxation is implemented by using force-bias Monte Carlo steps. Force bias MC involves displacement of all vertex of a cluster in the direction of distorting force. A set of 500 MC steps are carried after such intra cluster distortion. The detailed description of algorithm is illustrated in owchart, Figure 5.

4.8

Simulation details

In each simulation an ensemble of 1000 randomly congured monomers were taken in cubic box of 104 A at 300 K. Equilibrium moved was necessary to generate random conguration of monomer. In equilibrium move all but reaction moves were performed. Total of 1 105 equilibrium steps were performed. Wherein, 1 step is dened as set of moves to displace all of its particle once, which is the size of the system, N ( 1 MC step = 1000 MC moves). Reaction moves were included after equilibration of system was completed. All moves with predened probability of occurrence were considered. Probability of carrying out particular move depends on two main factor. Firstly, since movement of entire tetrahedral is more important than individual atoms, tetrahedral moves has highest probability. Secondly, system was diluted (5% mole) to compare with experimental outcomes, leading to low probability of reaction to occur. Hence, probability of reaction moves were kept very low. Detailed conguration of system and probabilities of dierent moves are tabulated in Table 2.

Results and Discussion

Although the purpose of this report was to reproduce the simulation results of work of Malani et al. 11 , it also includes the comparison with experimental work by Devreux et al. 16 Conventionally, Qn distribution is mapped to probe silica polymerization, which is performed by S i29 NMR study for each sampling. The work presented 11 , relates physical time with MC step, starting from common reference.

11

Start

Select a random OH1

Calculate cluster size, Ncl

Calculate p1,p2 and p3

Select a random no, R

Yes

R < p1?

No

Select OH2 from other cluster


Yes

R < p1+p2?
Select OH2 within reaction cutoff No

Select OH2 outside reaction cutoff, within the cluster

Replace OH1 and OH2 with BO

Accept the reaction with corrected probability, else reject

Perform force-bias if required

End

Figure 5: Flowchart for reaction move

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Table 2: Simulation details Parameter / Probabilities Box size (lx,ly,lz Angstrom) Temperature (K) Equilibrium rate constant, Keq Vertices displacement Tetrahedra displacement Tetrahedra rotation (Random) Tetrahedra rotation (Directional) Cluster displacement Cluster rotation Reaction moves Value 104,104,104 300 500 0.2 (0.1+0.24)=0.34 (0.05+0.12)=0.17 (0.05+0.12)=0.17 0.05 0.05 (0.01+0.01)=0.02

The common point considered was crossing of Q0 and Q1 proles, which occurs around 0.1 hr., experimentally and 148 MC in simulation. This point occurs at 165 MC in current reproduction of work. Subsequent crossing over points are compared to establish relationship between physical time and MC steps. The comparison is illustrated on Figure 6. Initial crossing over of Q0 and Q1 is slower than original work but after generation of Q2 , the entire polymerization process is accelerated. The last crossing over point between Q2 and Q4 was obtained before 104 MC steps, suggesting accelerated rate kinetics. The explanation for such behaviour would be in distribution of probabilities for various moves. The total probability of tetrahedral displacement was considered as 0.34, which is split into 0.1 for free tetrahedron and 0.24 for bonded tetrahedron. Same is true for rotation moves. Suggesting, free tetrahedron, which were initially present had a less probability for moves than in latter stage, where, tetrahedron are bonded. This explain why rst cross over point was obtained late and subsequent points were obtained early. To avoid issue related to dierent MC steps and physical time of the system, Qn distribution against degree of condensation was plotted, illustrated in Figure 7. The crossing over points, obtained in this work, takes place at higher degree of condensation. This suggest faster reaction in this work. Apart from this discordance, overall trend agrees with original work. The evaluation of cluster size, gives insight about stage of polymerization. The 13

Figure 6: Evaluation of Qn during polymerization, a) Current work, b) Original simulation 11 , c) Experiments of Devreux et al. 16 14

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Figure 7: Variation of Qn as a function of degree of condensation, a) Current work, b) Original simulation 11 , c) Experiments of Devreux et al. 16

average and maximum cluster size distribution are plotted in Figure 8. The trend can be divided into three main parts based on change in slopes of the trends. This division leads to dierent stages of silica polymerization.

Figure 8: Evaluation of average and maximum cluster size during MC simulation. Region I, II, III corresponds to oligomerization, ring formation and cluster aggregation stages of polymerization, respectively. 1. Oligomerization (0-1000 MC steps) The initial part of polymerization leads to formation of various oligomers such as dimer, dimer-monomer, dimer-dimer etc. The oligomerization is followed by cluster-cluster aggregation or cross linking. 2. Ring formation (1000-3400 MC steps) Small change in slope can be observed, in this region Q1 decreases where as Q2 and Q3 increases, indicates that cross linking is taking place. This also leads to formation of ring structure. 3. Cluster-cluster aggregation (3400- 6000 MC steps) Sharp change in the trend is observed in this region. Average and maximum cluster size both increases indicates drastic agglomeration of cluster. At this stage cluster-cluster aggregation takes place until one single cluster is obtained.

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4. Gel ageing ( 6000 MC steps) This stage occurs after one single cluster is obtained. In this stage, degree of condensation obtained is 0.8 and not completely 1. Hence, there is scope of forming cross-linking bonds among species. This leads to strengthening of overall silica structure.

Future plans

Since, this model mimics the experimentally obtained data, could be used to study the silica system. This model can be further develop to explore parameters inuencing nano structure arrangement of silica aerogel. This can be used to control the silica polymerization and to obtain a desire property of aerogel such as, enhancing CO2 capture capacity. Therefore future plans for this research can be formulated as; To, understand the silica polymerization system with parameter aecting various polymerization pathway. device a protocol to synthesis aerogel of desired properties by optimizing over desired pathway. enhance aerogel capacity to capture CO2 .

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[13] B. P. Feuston and S. H. Garofalini. Oligomerization in silica sols. The Journal of Physical Chemistry, 94(13):53515356, 1990. [14] R Astala, Scott M Auerbach, and PA Monson. Density functional theory study of silica zeolite structures: Stabilities and mechanical properties of sod, lta, cha, mor, and m. The Journal of Physical Chemistry B, 108(26):9208 9215, 2004. [15] J.C.G. Pereira, C.R.A. Catlow, G.D. Price, and R.M. Almeida. Atomistic modeling of silica based sol-gel processes. Journal of Sol-Gel Science and Technology, 8(1-3):5558, 1997. [16] F. Devreux, J. P. Boilot, F. Chaput, and A. Lecomte. Sol-gel condensation of rapidly hydrolyzed silicon alkoxides: A joint 29 Si nmr and small-angle x-ray scattering study. Phys. Rev. A, 41:69016909, Jun 1990.

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