Properties of aqueous alkaline sodium borohydride solutions and - PowerPoint PPT Presentation

Properties of aqueous alkaline sodium borohydride solutions and by-products formed during hydrolysis presented at the HYATT REGENCY SAN FRANCISCO AT EMBARCADERO CENTER BOARD ROOM B, ATRIUM LEVEL 5 EMBARCADERO CENTER SAN FRANCISCO, CA 94111 Session 1:00 - 6:00 PM by Don Gervasio, Michael Xu and Evan Thomas Arizona State University Tempe, AZ AUGUST 17, 2005 Applied Nano Bioscience Center at ASU

Outline • Review of ASU tasks • Identity of product of borohydride hydrolysis, NaB(OH) 4 • Solubility of hydrolysis product in aqueous solutions • Future Research • Characterizing hydrolysis by- products • Identity • Solution properties • Chemical vs electrochemical hydrolysis of borohydride • Seeking Polybenzimidazole (PBI) from PEMEAS for fuel cell membrane • Conclusions Applied Nano Bioscience Center at ASU

Review of ASU tasks Task 1: ASU will support the Univ. of Illinois (UIUC) in reporting and participate in technical meetings. Task 4.3: Optimize NaBH 4 performance Task 4.3.1: ASU will develop an energy dense (>2100 Wh/liter or Wh/Kg) hydrogen storage solution component consisting of >30% sodium borohydride in aqueous >1M NaOH solution. Task 4.3.2: ASU will develop a means of separating the hydrogen gas from the liquid hydrogen storage solution, so that only the hydrogen gas is supplied to the fuel cell anode. _____________________________________ Today’s talk relates to Tasks 4.3, -maximizing hydrogen storage & optimizing fluidics, -and is about boron-oxide identity and solution stability. Future work will try to determine - if the boron oxides that form during direct oxidation of borohydride on Pt is different from the oxides that form from heterogeneous catalysis (Ru) of borohydride hydrolysis. -Setting up an electrolysis cell and in situ electrochemical NMR cell for this purpose Applied Nano Bioscience Center at ASU

Current Research OVERALL GOAL: Maximize hydrogen storage capacity of aqueous alkaline sodium borohydride solution and solubility of hydrolysis by-product solution. NaBH 4 + 2 H 2 O → 4 H 2 + NaBO 2 Hydrolysis of Borohydride: SUB-GOALS: * Characterize hydrolysis of sodium borohydride (NaBH 4 ) using: - 11 B Nuclear Magnetic Resonance (NMR) Spectroscopy - X-ray diffraction (XRD) - Fourier Transform Infrared (FTIR) spectroscopy. *Ascertain the chemical structure of the by-product(s) formed during hydrolysis. *Determine the mechanism of the catalytic hydrolysis of NaBH4 in alkaline solution *Evaluate the effect of additives on: - the hydrolysis of sodium borohydride and the - solubility of the resulting boron-oxide by-products. Applied Nano Bioscience Center at ASU

Precipitates during catalytic hydrolysis Ru on alumina Not Stable in aqueous alkaline sodium borohydride hydrogen-storage solution ! Ru on various metal supports Ti best support: - stable - Ru adheres. Ru on metal Ti support is stable in Alumina-borate solid lump that forms in aqueous alkaline sodium borohydride hydrogen generation reactor from alumina solution! dissolution 30wt% sodium borohydride in aqueous 1 M NaOH solution. Question…Do sodium borohydride and hydrolysis by-products stay in solution? Or Precipitate? Applied Nano Bioscience Center at ASU

Answer…it depends on hydrolysis by-product(s) Possible By-Products formed during NaBH 4 Hydrolysis The reaction of hydrogen generation from sodium borohydride is nominally written as: NaBH 4 + 2 H 2 O → 4 H 2 + NaBO 2 Actually many boron oxides can form, dictating the amount of water needed as seen below . Boron Oxide Mole Oxygen H 2 O Needed Volume H 2 O (per NaBH 4 ) (30% sol’n) (milliliter) * NaB(OH) 4 4 moles 32 moles 576 . x H2O NaBO 2 2+x 16 288 Na2B4O7 7/2 28 504 . 10 H2O Na 2 B4O 7 17/2 68 1224 . 3 H 2 O Na 2 B 4 O 6 (OH) 2 11/2 44 792 . 5 H 2 O Na 2 B 4 O 7 12/2 48 864 . 3 H 2 O Na 2 B 4 O 5 (OH) 4 12/2 48 864 . 8 H 2 O Na 2 B 4 O 5 (OH) 4 17/2 68 1224 __________________ * ASU X-ray diffraction data indicate that NaB(OH) 4 is the by-product of hydrolysis reaction. Applied Nano Bioscience Center at ASU

XRD of Hydrolysis Product Hydrolysis product Same as NaB(OH) 4 Applied Nano Bioscience Center at ASU

Synthesis of NaB(OH)4 from boric acid B(OH) 3 + NaOH → NaB(OH) 4 Stoichiometric reaction done in water or water–tetrahydrofuran (THF) mixtures Precipitate Filter XRD of the product of this synthesis is same as NaB(OH)4 standard which is same as borohydride hydrolysis product last slide Applied Nano Bioscience Center at ASU

NMR of NaB(OH)4 7.0 -17.163 -19.068 6.0 Standard NaB(OH)4 -17.2 ppm 5.0 4.0 3.0 2.0 1.0 0.0 1.00 0.91 -1.0 0 -10 -20 -30 ppm (f1) NMR Figure 1 : B 11 NMR, presumably NaB(OH)4 with BF3 diethyl etherate in external capillary Applied Nano Bioscience Center at ASU

NMR of Borohydride Hydrolysis Product -59.712 -61.600 -17.374 -59.083 -60.341 -60.970 3000 -17.4 ppm 2500 2000 1500 1000 500 0 1.00 0.08 0 -10 -20 -30 -40 -50 -60 ppm (f1) B 11 NMR, 30% NaBH4 w/ Ru catalyst in situ after 3 weeks Applied Nano Bioscience Center at ASU

NMR Spectrum of Sodium Metaborate, Na BO 2 -16.578 -19.279 700 600 500 Not NaBO 2 -16.5 is not close to -17.2 400 BF 3 300 200 100 0 0.06 1.00 -5.0 -10.0 -15.0 -20.0 -25.0 ppm (f1) 11 B NMR, neat BF 3 diethyl etherate in external capillary and 0.05M NaBO 2 ·4H 2 O, 5% D 2 O in sample tube. Boric acid: 0 ppm. Applied Nano Bioscience Center at ASU

Conclusion on Identification of Borohydride Hydrolysis Product NMR like XRD indicates hydrolysis product if NaB(OH)4 Will do thermal analysis next to confirm match Applied Nano Bioscience Center at ASU

Oxide Identity and Solubility Tests Since solution NMR is in agreement with X-ray scattering of solids, that both techniques indicate that NaB(OH)4 is the principal oxide from the hydrolysis of 10 to 30% NaBH4 in aqueous 1 M NaOH, we accelerate studies of solubility by direct synthesis of NaB(OH)4 and testing of its solubility. Continuing solubility tests of NaB(OH)4 - air dry & weigh solid NaB(OH)4 - place in “solvent” - warm, stir - filter - air dry and reweigh - solubility is weight loss/volume of solvent Applied Nano Bioscience Center at ASU

Synthesis of NaB(OH)4 from boric acid B(OH) 3 + NaOH → NaB(OH) 4 Stoichiometric reaction done in water or water–tetrahydrofuran (THF) mixtures Precipitate Filter XRD of the product of this synthesis is same as NaB(OH)4 standard which is same as borohydride hydrolysis product last slide Applied Nano Bioscience Center at ASU

Hydrogen Content of alkaline sodium borohydride solutions - Goal: use as high a concentration of borohydride in solution as possible Gravimetric storage density: % H2 by weight Solid NaBH4 10.6 % NaBH4-20 solution (20 wt% NaBH4, 3 wt% NaOH, 77 wt% H 2O) 4.3 % NaBH4-25 solution (25 wt% NaBH 4, 3 wt% NaOH, 72 wt% H2O) 5.3 % NaBH4-30 solution (30 wt% NaBH 4, 3 wt% NaOH, 67 wt% H2O) 6.4 % NaBH4-35 solution (35 wt% NaBH4, 3 wt% NaOH, 62 wt% H2O) 7.5 % Volumetric storage density: 1 Liter NaBH4-20 solution 44 grams or 526 Standard Liters 1 Liter NaBH 4-25 solution 55 grams or 658 Standard Liters 1 Liter NaBH4-30 solution 66 grams or 789 Standard Liters 1 Liter NaBH4-35 solution 77 grams or 921 Standard Liters From Millenium Cell website, www.milleniumcell.com Applied Nano Bioscience Center at ASU

Solubility of Sodium Borohydride in Various Solvents From Rohm and Haas Borohydride digest www.Rohm&Haas.com For all liquid reactor, solubility of NaB(OH)4 not NaBH4 may be critical! Applied Nano Bioscience Center at ASU

Solubility Testing of NaB(OH)4 Solubility of NaB(OH) 4 in Various Solvents At Room Temp. Sample Solvent Amt. (mL) Solid Wt. (g) Undissolved Solid Collected (g) Solubility Limit (g/50mL) Solubility Limit (g/L) H 2 O 50 10.017 7.2637 2.7533 55.066 0.1M NH 4 OH 50 9.9978 7.1196 2.8782 57.564 29.2wt% NH 4 OH 50 9.9968 7.6224 2.3744 47.488 0.1M NaOH 50 9.9982 7.5556 2.4426 48.852 At Elevated Temp. (40ºC) Sample Solvent Amt. (mL) Solid Wt. (g) Undissolved Solid Collected (g) Solubility Limit (g/10mL) Solubility Limit (g/L) H 2 O 10 2.0056 0.6650 1.3406 134.060 0.1M NH 4 OH 10 2.0606 0.7379 1.3227 132.270 29.2wt% NH 4 OH 10 2.0150 1.5155 0.4995 49.950 0.1M NaOH 10 2.0200 1.2629 0.7571 75.710 H 2 O w/ 2% 90k CMC polymer 10 2.0229 0.8689 1.1540 115.400 0.1M NaOH w/ 2% 90k CMC polymer 10 2.0054 1.3401 0.6653 66.530 1M NH 4 OH NEXT 20wt% NH 4 OH Applied Nano Bioscience Center at ASU

Status: Hydrolysis of 30% NaBH 4 to NaB(OH) 4 Recall: in 1 000 g of fuel (NaBH4-30), there are: - 2.8 g NaOH or 0.07 moles of NaOH per kilo of solution - 700 g H 2 O or 39 moles of free water per kilogram of solution. - 300 g NaBH 4 or 8 moles of NaBH 4 per kilo of solution. NaBH 4 + 4 H 2 O → 4 H 2 + NaB(OH) 4 After the above hydrolysis reaction of 30wt% borohydride solution, there are: - 32 moles or 57 1 g of water consumed - 8 moles or 807.5 g of NaB(OH) 4 formed - 0.07 or 2.8 g of NaOH remain - 1 25 ml of free water remains. Questions for Future Work Q 1 : Is NaB(OH) 4 the only hydrolysis by-product? A: Yes Q2: Can 800 g of NaB(OH) 4 dissolve in 1 25 ml of pure water? With 0.07 moles of NaOH? A: Water or base does not seem to matter but this is work in progress Q3: Does the hydrolysis process influence identity of by-product(s)? - heterogeneous catalytic hydrolysis over Ru? (NMR ex-situ and in-situ) - electrolysis on Pt electrode? (NMR ex-situ and in-situ) A: work in progress Applied Nano Bioscience Center at ASU