Hydrogen Production from Deliquescence of Ammonia borane in Presence of Light-weighted Catalysts

Chang-Chen Chou (周昶辰)

1

, Cheng-Hong Liu (劉政宏)

1

, Bing-Hung

Chen (陳炳宏)

1,

* and Duu-Jong Lee (李篤中)

2

1_{Department of Chemical Engineering, National Cheng Kung University, Tainan,}

TAIWAN

2_{Department of Chemical Engineering, National Taiwan University of Science and}

Technology, Taipei, TAIWAN

Hydrogen Production from Deliquescence 

of Ammonia borane in Presence of        

Light‐weighted Catalysts

Date: February 24th_, 2012 1

Outline

Outline

Introduction

‒

_{Hydrogen energy}

‒

_{Hydrogen storage} 

‒

_{Chemical hydrides}

‒

_{Ammonia borane (NH}

₃

_BH

₃

_or AB)

Experiment

‒

_{Preparation of Co}

2+

_{/IR‐120 catalysts}

‒

_{Experimental setup}

‒

_{Scheme of experiment procedures}

Results and Discussion

‒

_{Solid‐state NH}

₃

_BH

₃

_composite

‒

_{Profiles and conversion}

‒

_{Hydrolysate analysis}

Conclusions

2

Introduction

The e missio n of C O2 Ref. http://china.usc.edu/ShowArticle.aspx?articleID=1543&AspxAutoDetectCookieSupport=1 Ref. http://www.ifw-dresden.de/institutes/imw/sections/21/funct-magn-mat/hydrogen-storage Energy consu mption

Hydrogen Energy

4

Hydrogen Storage

High-pressure tanks

‒ _{Compressed hydrogen tanks at 5,000 psi (~35 MPa) and} 10,000 psi (~70 MPa) have been certified worldwide.

Liquefied hydrogen

‒ The energy density of hydrogen can be improved by storing hydrogen in a liquid state.

Metal hydrides

‒ Conventional high-capacity metal hydrides require high temperatures (300 to 350C) to liberate hydrogen, but sufficient heat is not generally available in fuel cell transportation applications.

Chemical hydrides

‒ Commonly reactions involve chemical hydrides with water or alcohols, called hydrolysis reactions, to produce hydrogen.

Ref. http://www.eoearth.org/article/Hydrogen_storage

Hydrogen Storage (Physical Storage)

High-pressure tanks

‒ _{Compressed hydrogen tanks at 5,000 psi (~35 MPa) and} 10,000 psi (~70 MPa) have been certified worldwide.

Liquefied hydrogen

‒ The energy density of hydrogen can be improved by storing hydrogen in a liquid state.

Ref. http://www.eoearth.org/article/Hydrogen_storage

Ref. Eberle U et al., Chemical and physical solutions for hydrogen storage, Angewandte Chemie International Edition,48, 6608-6630 (2009)

Metal Hydrides for Hydrogen Storage

Ref. http://www.eoearth.org/article/Hydrogen_storage

Ref. Annemieke et al., Materials for hydrogen storage: current research trends and perspectives, Chemical Communications, 668-681 (2008)

Metal hydrides

‒ _{Conventional high-capacity metal hydrides require high} temperatures (300 to 350 C) to liberate hydrogen, but sufficient heat is not generally available in fuel cell transportation applications. Gravimetric density:  CoNi₅ H₆ : 1.1%  LaNi₅ H₆ : 0.9%  low  MgH₂ : 7.6%  Decomposition temperature too high 7

Chemical hydrides

‒ _{Commonly reactions involve chemical hydrides with water} or alcohols, called hydrolysis reactions, to produce hydrogen.

Ref. http://www.eoearth.org/article/Hydrogen_storage

Ref. http://www.sigmaaldrich.com/technical-documents/articles/material-matters/recent-developments.html

Ref. Z.P. Li et al., Protide compounds in hydrogen storage systems, Journal of Alloys and Compounds 359-357, 469-474 (2003)

Chemical Hydrides for Hydrogen Storage

The advantages of Chemical hydrides:

‒ _{Higher purity of produced hydrogen}

‒ _{Less energy-loss}

‒ _{Lower operation pressure}

Ref. https://efree.gl.ciw.edu/content/molecular-hydrogen-storage-light-element-compounds

Ref. C.H. Liu et al., Novel fabrication of solid-state NaBH4 /Ru-based catalyst composites for hydrogen evolution using a high-energy ball-milling process, Journal of Power

Sources 195, 3887-3892 (2010)

Ref. Catalysis in hydrolysis of sodium borohydride and ammonia borane, and electrocatalysis in oxidation of sodium borohydride, Catalysis Today 170, 1-2 (2011)

H₂ can be released from hydrolysis of NaBH₄ and NH₃ BH₃ could proceed at room temperature. Both hydrolysis reactions can be catalyzed by acids (liquid or solid) or metal catalysts. NaBH₄ NH₃ BH₃ Gravimetric density (wt %) 10.8 19.6

Chemical Hydrides for Hydrogen Storage

Ammonia borane (NH

₃

BH

₃

or AB)

The advantages of NH

₃

BH

₃

:

‒

The inherent hydrogen storage capacity of NH

₃

BH

₃

is

19.6 wt%.

‒

NH

₃

BH

₃

and its spent product after hydrolysis reaction

are rarely toxic and stable.

‒

Long-term storage stability.

 More than 80 days stable in aqueous solution under an argon atmosphere.

‒

The smallest volume occupied for hydrogen supply.

 6.57 mL for NH₃ BH₃ relative to 7.5 mL for NaBH₄ and 36 mL for liquefied hydrogen at 34 MPa to supply the same amount of hydrogen.

Ref. C.H. Liu et al., Hydrogen generated from hydrolysis of ammonia borane using cobalt and ruthenium based catalysts, International Journal of Hydrogen Energy 37, 2950-2959 (2011)

Ammonia borane (NH

₃

BH

₃

or AB)

Methods of produce hydrogen from NH

₃

BH

₃

‒

_{Solid-state thermolysis:}

‒

Transient-metal catalyzed dehydrogenation

‒

Ionic liquid catalyzed dehydrogenation

‒

_{Hydrothermolysis (thermolysis in solution phase)}

‒

_Hydrolysis:

3 3

2

2

3

2 4 2 catalyst

NH BH



H O



H



NH





BO



















500

 

₂ 2 150 ~ 2 2 2 2 2 110 ~ 3 3

nH

BN

HNBH

n

nH

HNBH

BH

NH

nH

BH

NH

BH

nNH

n C n C n n C





 







 







 



    11

Hydrogen production from NH

₃

BH

₃

hydrolysis:

‒

Proposed hydrolysis reaction of ammonia borane:

‒

Our previous work (in excess water):

3 3

2

2

3

2 4 2 catalyst

NH BH



H O



H



NH





BO

 3 3 3 2 2 3 3

BH

3

H

O

3

H

NH

H

BO

NH





catalyst

 









In this work, water is used as a limited reactant in

order to enhance gravimetric hydrogen storage

density.

Ref. C.H. Liu et al., Hydrogen generated from hydrolysis of ammonia borane using cobalt and ruthenium based catalysts, International Journal of Hydrogen Energy 37, 2950-2959 (2011)

Ammonia borane (NH

₃

BH

₃

or AB)

Experiment

Preparation of Co

2+

_{/IR-120 Catalysts}

CoCl₂ ·6H₂ O Amberlite IR-120

DI Water stirrin g 1 hr or m ore Rinsed by DI water

Put into the oven at 110C for 1 day

Co

Co

2+2+

_/IR

_/IR

_-

_-

_{120 catalysts}

_{120 catalysts}

chelating IR-120 SO₃- _H+ SO₃- _H+ + Co2+ SO₃ -SO₃ -Co2 + + 2H + 14

condenser H₂ + NH₃ H₂ condenser syringe mass flow meter computer thermocouple three-necked round-bottom flask cold water Solid-state NH₃ BH₃ composite

Experimental Setup

15 0.1N H₂ SO_{4 silica gel} particles

Scheme of Experimental Procedures

XRD patterns FT-IR spectra 11_{B NMR analysis} SEM images NH₃ BH 3

Co2+_/IR-120 Ball milling

DI water Hydrogen profile Temperature profile Hydrolysate solid-state NH₃ BH₃ composite 16

Results and Discussion

Solid-State NH

₃

BH

₃

Composite

Particles size: 20 to 30 μm

SEM images reveal that solid- state NH₃ BH₃ composites are

uniformly dispersed through high-energy ball milling.



SEM images

3 3

2

2

3

2 4 2

catalyst

NH BH



H O



H



NH





BO



Profiles and Conversion

No. H₂ O/AB Deionized water (g) Injection rate (g/hr)

(a) 1.28 0.149 0.745 (b) 1.28 0.149 1.118 (c) 2.57 0.300 0.938 (d) 2.57 0.300 1.406 (e) 4.50 0.524 1.048 (f) 4.50 0.524 1.572 19

(a)

(b)

(c) (e)

(d) (f)

Profiles and Conversion

20

Temperature increases  Hydrogen production increases.

No. H₂ O/AB Deionized water (g) Injection rate (g/hr) Conversion (%) (a) 1.28 0.149 0.745 0 (b) 1.28 0.149 1.118 0.56 (c) 2.57 0.300 0.938 61.89 (d) 2.57 0.300 1.406 70.78 (e) 4.50 0.524 1.048 100.00 (f) 4.50 0.524 1.572 100.00 3 3

2

2

3

2 4 2 catalyst

NH BH



H O



H



NH





BO



Profiles and Conversion

21

Conversion is calculated by the amount of produced hydrogen

recorded by a mass flow meter (MFM).

Hydrolysate Analysis



XRD patterns

2θ=15o _2θ=24o _2θ=29o 2θ=24o NH₃ BH₃ : 2

θ

=24o_. H₃ BO₃ : 2

θ

=15o _{and 2}

_θ

=28o_. HBO₂ : 2

θ

=13o _{and 2}

_θ

=29o_.

The hydrolysate might be either H₃ BO₃ or HBO₂ . Database of HBO₂ 29.011o 13.086o 21.161o (a) (b) (c) (d) (e) (f) NH₃ BH₃ H₃ BO₃ 22



FT-IR spectra

3200-3400 cm-1 O-H stretching 1330-1420 cm-1 O-H bending 1605 cm-1 N-H bending 1200, 1460 cm-1 B-O stretching 1063, 1160 cm-1 B-H torsion 727, 797 cm-1 B-N stretching 780 cm-1 B-O bending

(a) has B-N stretching, B-H torsion and N-H bending

bonding.  unreacted NH₃ BH₃ .

All of the hydrolysates have B-O bending, B-O

stretching, O-H bending

and O-H stretching bonding.  H_x B_y O_z .

The hydrolysate could be either H₃ BO₃ or HBO₂ . 727, 797 cm-1 B-N stretching 1605 cm-1 N-H bending 1063, 1160 cm-1 B-H torsion

Hydrolysate Analysis

(a) (b) (c) (d) (e) (f) NH₃ BH₃ H₃ BO₃ NaBO₂ 23



NMR spectra

-27 ppm _NH 3 BH3 NH₃ BH₃ NH₃ BH₃ 6.6 ppm 14.7 ppm 2.8 ppm BO₃3-_/BO 2 -BO₃3-_/BO 2- BO33-/BO2 -BO₃3-_/BO 2 -BO₃3-_/BO 2 -BO₃3-_/BO 2 -NH₃ BH₃ The peak at -27 ppm is NH₃ BH₃ .  (a) to (d) still have unreacted NH₃ BH₃ .

The other peak is the mixture of borate (BO₃3-₎ and metaborate (BO₂-_). The hydrolysate is the mixture of H₃ BO₃ and HBO₂ .

Hydrolysate Analysis

_{Reference: NaBH}

4

No. H₂ O/AB Deionized water (g) Injection rate (g/hr) Conversion by MFM (%) Conversion by NMR (%) (a) 1.28 0.149 0.745 0 42.12 (b) 1.28 0.149 1.118 0.56 57.21 (c) 2.57 0.300 0.938 61.89 72.46 (d) 2.57 0.300 1.406 70.78 93.70 (e) 4.50 0.524 1.048 100.00 100.00 (f) 4.50 0.524 1.572 100.00 100.00



Conversion by NMR is calculated from the area-under-

curve (AUC) of the NMR spectra

3 3

2

2

3

2 4 2

catalyst

NH BH



H O



H



NH





BO



Hydrolysate Analysis

Conversion by MFM: based on produced hydrogen.

Conversion by NMR: based on consumption of NH

₃

BH

₃

.

※The sensitivity of H

₂

MFM.

No. H₂ O/AB Deionized water (g) Injection rate (g/hr) Conversion by MFM (%) Conversion by NMR (%) (a) 1.28 0.149 0.745 0 42.12 (b) 1.28 0.149 1.118 0.56 57.21 (c) 2.57 0.300 0.938 61.89 72.46 (d) 2.57 0.300 1.406 70.78 93.70 (e) 4.50 0.524 1.048 100.00 100.00 (f) 4.50 0.524 1.572 100.00 100.00

Although H

₂

O/AB for (c) and (d) is 2.57 > 2, a conversion

efficiency of 100% is not achieved, as elevated temperature in

the reacting system, caused by exothermic reaction heat, gives

rise to evaporation of one of the reactants, i.e. water.

3 3

2

2

3

2 4 2

catalyst

NH BH



H O



H



NH





BO



Hydrolysate Analysis

26



Conversion by NMR is calculated from the area-under-

curve (AUC) of the NMR spectra

Conclusions

Solid-state NH

₃

BH

₃

composite is uniformly dispersed with

high-energy ball milling.

Temperature imposes a positive effect in the hydrolysis

reaction of ammonia borane for hydrogen production.

According to the XRD, FT-IR and

11

_{B NMR analyses, the}

hydrolysate is likely a mixture of H

₃

BO

₃

and HBO

₂

.

The hydrolysis reaction of the solid-state NH

₃

BH

₃

composite could be revised as

Conclusions

3 3 2

3

2 3 3

2

3

catalyst

NH BH



zH O





H



x

H BO



yHBO



NH



Thanks for your attention !

Back‐up materials

The applications of Hydrogen energy

Ref. http://www.ridelust.com/doe-cuts-fuel-cell-funding-for-cars/

Ref. http://energy.gov/articles/hydrogen-student-design-contest-inspires-and-opens-doors

Ref. A. Kirubakaran et al., A review on fuel cell technologies and power electronic interface, Renewable and Sustainable Energy Reviews 13, 2430-2440 (2009)



Anode reaction:



Cathode reaction:



Overall reaction:

-2

2

2

H



H





e

-2 2

1/ 2

O



2

H





2

e



H O

2

1/ 2

2 2

H



O



H O

31

Solid-state NH

₃

BH

₃

composite

Element Weight% Atomic%

B 39.34 46.34

N 58.50 53.19

Co 2.16 0.47

Totals 100.00

(a) EDS spectra (b) EDS mapping images

B

N Co

Analysis of the hydrolysate



Fitting curve

The chemistry

of hydrolysate

is the mixture

of H

₃

BO

₃

and

HBO

₂

.

33