Electrons, Protons, and Solvents in Carbon Nanotubes by Gregory Arthur Pilgrim

171 Pages·2015·24.8 MB·English

by  Greg Pilgrim

Electrons,
 Protons,
 and
 Solvents
 in
 Carbon
 Nanotubes

by

Gregory
 Arthur
 Pilgrim

Submitted
 in
 Partial
 Fulfillment

of
 the

Requirements
 for
 the
 Degree

Doctor
 of
 Philosophy

Supervised
 by

Professor
 Todd
 D.
 Krauss

Department
 of
 Chemistry

Arts,
 Sciences
 and
 Engineering

School
 of
 Arts
 and
 Sciences

University
 of
 Rochester

Rochester,
 NY

2015
ii

This
 thesis
 is
 dedicated
 to
 the
 graduate
 students
 of
 the
 Laboratory
 for
 Electronic

Ceramics
 at
 Alfred
 University.

 For
 the
 last
 twenty
 years
 I’ve
 wanted
 to
 be
 as
 cool
 as

you.

“…and
 he
 that
 will
 not
 apply
 new
 remedies
 must
 expect
 new
 evils;
 for
 time
 is
 the

greatest
 innovator;
 and
 if
 time
 of
 course
 alter
 things
 to
 the
 worse,
 and
 wisdom
 and

council
 shall
 not
 alter
 them
 to
 the
 better,
 what
 will
 be
 the
 end?”

Sir
 Francis
 Bacon,
 1625
iii

Biographical
 Sketch

  The
 author
 was
 born
 in
 Columbia,
 Maryland
 on
 August
 25th
 1988.

 He

attended
 Rochester
 Institute
 of
 Technology
 from
 2006
 to
 2009
 and
 Alfred

University
 from
 2009
 to
 2010.

 He
 graduated
 from
 RIT
 with
 a
 Bachelor
 of
 Science

degree
 in
 Chemistry
 in
 2010
 after
 which
 he
 began
 graduate
 studies
 at
 the
 University

of
 Rochester.

 He
 received
 his
 Masters
 degree
 in
 Chemistry
 in
 2012.

 Throughout
 his

graduate
 career
 he
 has
 been
 advised
 by
 Professor
 Todd
 Krauss.

 He
 was
 awarded
 a

Weissberger
 Fellowship
 in
 2014.

 While
 at
 the
 University
 of
 Rochester
 he
 has

published
 one
 paper
 and
 submitted
 one
 patent.

Publications

Gregory
 A.
 Pilgrim,
 Joanne
 W.
 Leadbetter,
 Fen
 Qiu,
 Anni
 J.
 Siitonen,
 Steven
 M.

Pilgrim,
 and
 Todd
 D.
 Krauss,
 “Electron
 Conductive
 and
 Proton
 Permeable
 Vertically

Aligned
 Carbon
 Nanotube
 Membranes”
 Nano
 Lett.,
 2014,
 14
 (4),
 pp
 1728–1733

Gregory
 A.
 Pilgrim,
 Amanda
 R.
 Amori,
 Zhentao
 Hou,
 Fen
 Qui,
 Todd
 D.
 Krauss,

“Simultaneous
 Evaluation
 of
 Proton
 and
 Electron
 Crossing
 In
 Carbon
 Nanotube

Membranes”
 In
 Preparation

Gregory
 A.
 Pilgrim,
 Chae
 Un
 Kim,
 Surendra
 K.
 Gupta,
 Sol
 M.
 Gruner,
 Todd
 D.
 Krauss,

“Observation
 of
 Tetragonal
 Ice
 Confined
 in
 Carbon
 Nanotubes”
 In
 Preparation
iv

Patent
 Pending

Membranes
 With
 Vertically
 Correlated
 Carbon
 Nanotubes,
 And
 Methods
 Of
 Making

And
 Using
 Same,
 Patent
 Application
 Number
 61/945,439
v

Acknowledgements

First
 and
 foremost
 I
 would
 like
 to
 say
 a
 massive
 thank
 you
 to
 my
 groupmates.

It’s
 you,
 individually
 and
 collectively,
 that
 I’ve
 spent
 the
 last
 five
 years
 with,
 and
 it’s

you
 that
 have
 made
 those
 years
 so
 pleasant.

 It’s
 been
 our
 discussions
 that
 have

formed
 my
 views
 of
 what
 a
 scientist
 ought
 to
 be,
 and
 do.

 To
 Michael
 Odoi
 in

particular,
 a
 source
 of
 insight
 and
 wisdom
 where
 it
 was
 sorely
 needed,
 a
 special

thanks
 is
 due.

 To
 Sanela
 Lampa-­‐Pastrik,
 for
 her
 insightful
 and
 speedy
 contributions

to
 the
 assembly
 of
 this
 work,
 a
 large
 thank
 you
 is
 due
 as
 well.

Next,
 thank
 you
 to
 my
 advisor,
 Todd
 Krauss.

 Todd
 kept
 the
 bills
 paid
 for
 the

past
 five
 years,
 no
 small
 accomplishment
 in
 the
 current
 funding
 climate,
 and
 one
 I’m

very
 grateful
 for.

 Todd
 also
 gave
 me
 significant
 leeway
 to
 look
 into
 things
 that

interested
 me.

 Sometimes
 those
 things
 bore
 fruit,
 other
 times
 not.

 In
 any
 case
 I’m

grateful
 for
 the
 chance
 to
 have
 looked.

To
 my
 collaborators,
 of
 which
 there
 are
 many,
 a
 thank
 you
 for
 your
 uniting

features:
 a
 willingness
 to
 help,
 and
 a
 patience
 with
 me
 as
 I
 learned.

 I
 would

particularly
 like
 to
 thank
 Brian
 McIntyre
 of
 URnano,
 for
 his
 patience,
 his
 good

humor,
 and
 for
 his
 efforts
 on
 behalf
 of
 my
 endeavors.

 Similarly,
 the
 staffs
 of
 the

Cornell
 Nanoscale
 Facility,
 the
 Institute
 for
 Electronics
 and
 Nanotechnology
 and
 the

Cornell
 High
 Energy
 Synchrotron
 Source
 have
 all
 been
 exceedingly
 kind
 to
 me,
 and

patient
 with
 my
 less-­‐than-­‐orthodox
 ideas
 for
 their
 equipment.

 Thank
 you
 all.

To
 the
 staff
 of
 the
 Chemistry
 Department,
 who
 provided
 the
 underlying

structure
 for
 all
 of
 this,
 a
 big
 thank
 you.
vi

To
 the
 extended
 swimming
 community,
 including
 but
 not
 limited
 to,
 the

Rochester
 Monroe
 County
 Certified
 Swim
 Officials,
 the
 University
 of
 Rochester

Masters
 Swim
 Team
 swimmers
 and
 staff,
 and
 my
 friends,
 coaches,
 and
 teammates

from
 USA
 and
 NCAA
 Swimming,
 thank
 you
 for
 your
 camaraderie,
 enthusiasm,
 and

particularly
 for
 the
 perspective
 that
 comes
 with
 knowing
 that
 maintaining
 mental

focus
 is
 one
 thing
 but
 maintaining
 mental
 focus
 without
 breathing
 is
 quite
 another.

To
 the
 Baldwins,
 your
 interest
 in,
 and
 enthusiasm
 for,
 my
 work
 has
 been
 a

great
 encouragement
 throughout
 this
 process.

 Thank
 you
 very
 much.

To
 my
 parents,
 your
 involvement
 in
 all
 of
 this
 is
 less
 concrete,
 but
 crucial
 just

the
 same.

 What
 you’ve
 done,
 and
 been,
 for
 me
 belies
 description
 but
 underpins

everything
 I
 do,
 including
 this
 work.

 Thank
 you.

And
 finally
 to
 Caitlin,
 it’s
 been
 a
 great
 five
 years,
 let’s
 have
 many,
 many
 more!
vii

Abstract

The
 two
 regimes
 of
 carbon
 nanotubes
 –
 wall
 and
 bore
 –
 provide
 two
 distinct

environments.

 The
 extended
 pi
 structure
 of
 nanotube
 walls
 was
 used
 to
 transport

electrons
 at
 energy
 levels
 dependent
 on
 the
 wall
 chirality.

 The
 empty
 bore
 was
 used

to
 host
 solvent
 molecules
 and
 provide
 a
 pathway
 for
 proton
 transport.

Simultaneous
 transport
 of
 both
 charged
 species
 was
 measured
 in
 a
 donor-­‐acceptor

system
 inspired
 by
 photosynthesis
 in
 plants
 and
 aimed
 at
 storing
 solar
 energy
 in

chemical
 fuel.

 Transport
 was
 observed
 spectroscopically
 through
 use
 of
 indicator

molecules.

 The
 interaction
 of
 solvent
 molecules
 in
 the
 bore
 with
 the
 confinement

imposed
 by
 the
 walls
 was
 also
 probed
 by
 x-­‐ray
 diffraction
 at
 low
 temperature.

Confined
 molecules
 and
 their
 interactions
 have
 implications
 for
 areas
 as
 diverse
 as

protein
 folding
 and
 geology.
viii

Contributors
 and
 Funding
 Sources

Committee

Professor
 Todd
 Krauss,
 Departments
 of
 Chemistry
 and
 Optics

Professor
 Lisa
 DeLouise,
 Departments
 of
 Dermatology,
 Biomedical
 Engineering,
 and

Electrical
 and
 Computer
 Engineering

Professor
 Kara
 Bren,
 Department
 of
 Chemistry

Chair

Professor
 Hitomi
 Mukaibo,
 Department
 of
 Chemical
 Engineering

Contributors

Joanne
 Leadbetter
 assisted
 in
 the
 design
 and
 collection
 of
 voltage
 driven

proton-­‐crossing
 measurements
 described
 in
 Chapter
 2.

 Fen
 Qiu
 synthesized
 the

quantum
 dots
 used
 in
 Chapters
 2
 and
 3.

 Anni
 Siitonen
 assisted
 in
 the
 development

of
 the
 vertically
 aligned
 nanotube
 growth
 procedure
 described
 in
 Chapter
 2.

 Steven

Pilgrim
 assisted
 in
 the
 development
 of
 the
 epoxy
 impregnation
 method
 described
 in

Chapter
 2.

Amanda
 Amori
 and
 Zhentao
 Hou
 performed
 the
 nanotube
 solubilizations
 and

collected
 the
 spectroscopic
 information
 used
 to
 identify
 nanotube
 chirality

described
 in
 Chapter
 3.

 Michael
 Mark
 and
 Stephanie
 Daifuku
 built
 the
 Raman

system
 used
 in
 some
 measurements
 in
 Chapter
 3.
ix

  Chae
 Un
 Kim
 and
 Sol
 Gruner
 assisted
 with
 collection
 of
 the
 x-­‐ray
 diffraction

patterns
 described
 in
 Chapter
 4.

 Surendra
 (Vinnie)
 Gupta
 assisted
 with
 analysis
 of

the
 powder
 diffraction
 patterns
 described
 in
 Chapter
 4.

All
 work
 mentioned
 above,
 with
 the
 exception
 of
 quantum
 dot
 synthesis,

nanotube
 solubilization,
 and
 Raman
 system
 construction
 was
 carried
 out
 in
 direct

collaboration
 with
 Greg
 Pilgrim,
 the
 author
 of
 this
 thesis.

 All
 other
 work
 described

in
 this
 thesis
 was
 developed
 and
 carried
 out
 by
 Greg
 Pilgrim
 under
 the
 guidance
 of

Todd
 Krauss.

Funding
 Sources

This
 work
 was
 funded
 by
 the
 U.S.
 Department
 of
 Energy.

 Significant
 portions

of
 this
 work
 were
 performed
 at
 the
 Cornell
 Nanoscale
 Facility
 at
 Cornell
 University

and
 at
 the
 Institute
 for
 Electronics
 and
 Nanotechnology
 at
 Georgia
 Institute
 of

Technology,
 both
 of
 which
 are
 members
 of
 the
 National
 Nanotechnology

Infrastructure
 Network
 supported
 by
 the
 National
 Science
 Foundation.

 Chapter
 4

covers
 work
 performed
 at
 the
 Cornell
 High
 Energy
 Synchrotron
 Source
 at
 Cornell

University,
 which
 is
 also
 supported
 by
 the
 National
 Science
 Foundation.
x

Table
 of
 Contents

Dedication

  ii

Biographical
 Sketch

  iii

Acknowledgements

  v

Abstract

  vii

Contributors
 and
 Funding
 Sources

  viii

Table
 of
 Contents

  x

List
 of
 Tables

  xv

List
 of
 Figures

  xvi

List
 of
 Abbreviations

  xxxv

Chapter
 1:
 Introduction

  2

  1.1:
 Energy

  2

  1.1.1
 Energy
 Consumption

  2

  1.1.2
 Solar
 Power

  2

  1.1.3
 Transportation
 Fuel

  3

  1.1.4
 Solar
 Hydrogen

  4

  1.2
 Artificial
 Photosynthesis

  5

  1.2.1
 Background

  5

  1.2.2
 Charge
 Separation

  6

  1.2.3
 Water
 Splitting

  9