theory and computation working with...

Center for the Computational Design of Functional Layered Materials

THEORY AND COMPUTATION WORKING WITH EXPERIMENT TO UNDERSTAND AND IMPROVE

WATER SPLITTING CATALYSTS

Daniel StronginDepartment of ChemistryTemple UniversityPhiladelphia, PA

112017 EFRC-Hub-CMS PI Meeting 1

22017 EFRC-Hub-CMS PI Meeting

validate theory

H2O Oxidation (OER)2H2O → 4H+ + 4e− + O2 ; E° = 1.23 V (pH 0) vs. NHE

HHO

HHO OH

2H+ + 2e-

OH O

4H+ + 4e-

O

4H+ + 4e- + O2

2H+ + 2e− → H2 ; E° = 0 V (pH 0) vs. NHE

H+

H2e- H H2

H+

H2 Reduction (HER)

Can we use theory/computation to make layered materials more active for Water Splitting?


Motivations: 1) Validate Theoretical models while improving catalysts for the Oxygen evolution reaction (OER) and hydrogen Evolution reaction (HER)2) Split water for a hydrogen economy

4

Solar to fuel conversion

Light capture ElectrocatalysisSunlight Charge separation Fuels (H2 or CxHyOz)

High absorption Long diffusion lengths Minimal overpotential

• Solar farms- tethering PV device with electrolyzes(solar energy electricity fuels)

• Advance technologies (with single energy transformation)

Photo-anodes with electrocatalysts

(inefficient)

charge transport

Reece, Steven Y., et al. "Wireless solar water splitting using silicon-based semiconductors and earth-abundant catalysts." Science 334.6056 (2011): 645-648.


Birnessite

Often looked at as analogue of Mn4CaO4

Cluster of photosystem II (uses light to oxidize water to O2 and protons).

Birnessite is not a good catalyst for OER.

Can we make it better?

5

Lucht, et. al, J. Phys. Chem. C 2015, 119, 22838−22846


OER Literature Values for MnO2

Suib and coworkers, JACS, 136, 2014, 11452

Can we learnHow to make thisLayered materialMore active whileTesting theory/computation?B

est

Wo

rst

11 112017 EFRC-Hub-CMS PI Meeting

Vo

ltag

e re

qu

ired

fo

r O

ERm

inu

s 1

.23

V

Intercalation of cations

Unique environmentFor water oxidation

Four ways to alter reactivity of layered material

Defect, proportion ofMn(IV) to Mn(III)

Birnessite Modification

7

Interlayer distance


1.2 1.4 1.6 1.8 2.0

0

5

10

15

20

Cu

rre

nt D

en

sity (

mA

/cm

2)

3.46

3.78

3.7

3.39

0.0 0.2 0.4 0.6 0.8Overpotential / V

Potential / V (RHE)

Note the lower the average Mn oxidation state, the lower the overpotential (volts above 1.23 V, top axis).

AverageMnO2 oxidationstate. Perfect MnO2

would be 4.

Effect of metal oxidation state on overpotential


good

worst

birnessite

MnOOH

{[(1 ) / ] }[ ]

nF RT

oi i e

O

2P

rod

uct

Mn(III) in Birnessite

• Mn(III) in pure layered MnO2 can be understood as a small-polaron:

– Mn(IV) + e-Mn(III)

– self-trapping energy around -0.4 eV

• Mn(III) in birnessite can be understood as a defect-bound small-polaron

– Mn(IV) + K Mn(III) + K(I)


H. Peng

&J. Perdew

Redox properties of birnessite for catalysis: A defect perspective, Haowei Peng, Ian G. McKendry, Ran Ding, Akila C. Thenuwara, Qing Kang, Samantha L. Shumlas, Daniel R. Strongin, Michael J. Zdilla, and John P. Perdew, in review at PNAS

Importance of Mn(III)

10

Model treats Mn(III) as small polaron. Non-uniform distribution of Mn(III)-K+ dipole layer to layerleads to resonance between electron in eg

1 state and Mn(IV) [conduction band]. Accountsfor facile oxidation state changes for Mn undergoing catalytic cycles.

eg1

eg1eg

1

eg1

Redox properties of birnessite for catalysis: A defect perspective, Haowei Peng, Ian G. McKendry, Ran Ding, Akila C. Thenuwara, Qing Kang, Samantha L. Shumlas, Daniel R. Strongin, Michael J. Zdilla, and John P. Perdew, in review at PNAS

Mn4+ + e- Mn3+



Test TheoryBirnessite assembled layer by layer

Test TheoryBirnessite assembled layer by layer

• AOS: A = 3.85 and B = 3.52


B

B

A

A

A

A

A

A

3.52

3.52

3.85

3.85

3.85

e-

K+ GradientIn K+-e-

pairsK+e-

Mn(III)

Mn(IV) + e- Mn(III)

Zdilla Group

Intercalation of cations

Unique environmentFor water oxidation

Four ways to alter reactivity of layered material

Defect, proportion ofMn(IV) to Mn(III)

Birnessite Modification

13

Interlayer distance


✤ Molecular Dynamics calculations (GROMACS, CLAYFF)

&M. Klein

Hydration Structure of Ni in Interlayer

15

+

Cross-sectional view of ions in interlayer

+ +

Water molecule cannotAdopt unique lowest energyGround state.

Redox activecation

Water dipole


Can we make an OER catalyst even better

by confining it in the interlayer region of a

host material? Ni in birnessite

16

Thenuwara et al., Angewandte Chemie, International Edition (2016), 55(35), 10381-10385


Test MD Simulation Prediction

Ni-intercalated Birnessite preparation

Ni(II)-hydrazine complexes form when excess hydrazine is not used.I.e., when NiCl2 is used, Ni(N2H4)2Cl2 and Ni(N2H4)3Cl2 complexes form

We find that these complexes transport Ni(II) into the interlayer of MnO2Why this happens is being explored


Ni2+

MnO2

sheet

MnO2

sheet

Ni2+/Ni3+

2) Ni2+ is more easily oxidized to Ni3+ when in interlayer in agreement withtheory

Polarization curves showing activity of Ni confined to interlayer region

O2

Pro

du

ct1) Confining Ni to Interlayer lowersoverpotential


What about cobalt in birnessite?

19

Thenuwara, Akila C.; Shumlas, Samantha L.; Attanayake, Nuwan H.; Aulin, Yaroslav V.; McKendry, Ian G.; Qiao, Qiao; Zhu, Yimei; Borguet, Eric; Zdilla, Michael J.; Strongin, Daniel R., ACS Catalysis (2016), 6(11), 7739-7743


Does MD Simulation have broad Impact

0.8 1.0 1.2 1.4 1.6 1.8

0

20

40

60

80

100

Potential (V vs RHE)

Cu

rren

t D

en

sit

y (

mA

cm

-2) Birnessite

Co3O

4

-Co(OH)2

Co doped Birnessite

Co2+

/Birnessite

-Co(OH)2

20% Ir/C

-0.4 -0.2 0.0 0.2 0.4 0.6

Overpotential (V)

Co2+ to Co3+ oxidation

Co in birnessite

Co alone

Thenuwara, Akila C.; Shumlas, Samantha L.; Attanayake, Nuwan H.; Aulin, Yaroslav V.; McKendry, Ian G.; Qiao, Qiao; Zhu, Yimei; Borguet, Eric; Zdilla, Michael J.; Strongin, Daniel R., ACS Catalysis (2016), 6(11), 7739-7743


What about cobalt in FeNi double

Hydroxide?

21

Ni2+

Fe3+

Overpotential is 330 mVAt 10 mA/cm2


Can we extend our paradigm to other layered materials?

NiFe LDH as an effective OER catalyst

Song, Fang, and Xile Hu. "Exfoliation of layered double hydroxides for enhanced oxygen evolution catalysis." Nature communications 5 (2014).

Overpotential @ 10 mA cm-2 ~ 345 mV for bulk NiFe LDH


DFT: OER overpotential for Co in 2D sheets of LDH

23

Qimin yan


Heated at

150°C for

48 hr

anneal at

220°C for

4 hr

Ni-Fe-CO3- LDH

Ni-Fe mixed

metal oxide

Co2+

Co2+

Co2+

exposed to

1M Co2+

and stir for

48 hrs

Co intercalated

Ni-Fe-Cl- LDH

Also MD simulations predict enhancement if Co is in interlayer


Electrochemical investigation of Co modified NiFe LDH

Overpotential at 10 mA cm-2

for Co2+ intercalated NiFe LDH : 265 mV on GC

Co2+

Co2+

Co2+

Co in sheet


Catalyst η (mV) @

10mA/cm2

Tafel slope

(mV/dec)

TOF (s-1) @

300 mV, η

Cdl

(mF/cm2)

ECSA (m2/g) Roughnes

s Factor

Ni15Fe5 LDH 310±5 54±3 0.035 0.257143 2.31±0.2 6 ±1

Ni15Fe5Co2.5

LDH

290±12 52±5 0.0540.442857 4.04±0.5 11±3

Ni15Fe5Co3.5

LDH

312±10 55±3 0.0190.371429 3.42±0.3 9±2

Ni15Fe5Co4.5

LDH

314±5 56±5 0.0150.271429 2.53±0.3 7±2

Ni10Fe5Co5

LDH

322±5 58±4 0.0120.30512 2.74±0.1 7±1

Ni12.5Fe5Co2.

5 LDH

310±7 53±3 0.0190.257143 2.36±0.3 6±2

Ni13.75Fe5Co1

.25 LDH

312±9 54±4 0.0280.585714 5.39±0.3 15±2

Co2+

intercalated

NiFe LDH

265±5 47±3 0.106

0.328571 2.94±0.3 8±2

20% Ir/C 338±15 77±5 0.009 21.57143 80.32±1.5 539±12


Co insheet

Co ininterlayer

What about the HER on 1T MoS2?

27

2H+ + 2e- H2(g)


Theory Input on the Hydrogen evolution reaction (HER)


Top viewOf 2x2 supercell H on top of S atom on basal plane

1.362 Å

Top viewOf intercalated structure

Side viewOf intercalated structure

DFT to determine GH on 1T-MoS2

Effect of intercalated metals on the electrocatalytic activity of 1T-MoS2 for the hydrogen evolution reactionAttanayake, Thenuwara, Patra, Aulin, Tran, Chakraborty, Borguet, Klein, Perdew, and Strongin, submitted to Angewandte Chemie (2017)

29

GH0Best HER

DFT using SCAN is consistent with experimental results

Introductionof states bysp or d-metalenhances HER



30

Effect of Intercalation of different cations in interlayer space of MoS2

All cation intercalation lowers overpotential for HER

Bulk MoS2 exfoliatedand then reassembledinto layered material inthe presence of thecation of interest.


Nuwan Attanayake

31

GH0Best HER

DFT using SCAN is consistent with experimental results

Introductionof states bysp or d-metalenhances HER



SummaryTheory and Computation has helped guide the modification and explain the reactivity of layered electrocatalysts.

Placement of an already active OER catalyst in the interlayer region of a layered material can make the material even more active

Results have a broad impact with regard to improving the catalytic activity of other layered materials

32 3232 322017 EFRC-Hub-CMS PI Meeting


Acknowledgements

• Daniel Strongin – PI– Nuwan Attanayake– Qing Kang– Samantha Shumlas– Akila Chathuranga Thenuwara

• Jianwei Sun (SCAN) DFT• Rick Remsing (MD simulations)• Mike Klein• Michael Zdilla - PI

– Ian McKendry• Eric Borguet - PI

– Laszlo Frazer – Loranne Vernisse



34

END OF PRESENTATION

Extra slides follow

Mechanistic insight into oxygen evolution reaction(OER)

Ideal CatalystRuO2(110)

Rossmeisl, Jan, et al. "Electrolysis of water on oxide surfaces." Journal of Electroanalytical Chemistry 607.1 (2007): 83-89.

𝐇𝟐𝐎+ 𝐒 → 𝐎𝐇∗ +𝐇+ +𝐞−

𝐎𝐇∗ → 𝐎∗ +𝐇+ +𝐞−

𝐎∗ + 𝐇𝟐𝐎 → 𝐇𝐎𝐎∗ +𝐇+ +𝐞−

𝐇𝐎𝐎∗ → 𝐒 +𝐎𝟐+ 𝐇+ +𝐞−

ΔG10

ΔG20

ΔG30

ΔG40

3.2

eV

36

𝟐𝐇𝟐𝐎 → 𝐎𝟐+ 𝟒𝐇+ + 𝟒𝐞−

Friebel, Daniel, et al. JACS 137.3 (2015): 1305-1313.

• A significant OER activity enhancement that can be achieved with mixed (Ni,Fe)oxyhydroxides (Ni1−xFexOOH) over their pure Ni and Fe parent compounds. DFT predicts that Fe edge to be the active site for OER

(Ni,Fe)OOH for Electrocatalytic Water Splitting

Zhang, Bo, et al. Science 352.6283 (2016): 333-337.

Amorphous FeCoW oxyhydroxide for OER

Move to Double Hydroxides

overpoential at 10 mA cm-2: 223 mV on GC

38

rutiles

perovskites

Co3O4,NiO

MnyOx

Scaling relations

Man, Isabela C., et al. "Universality in oxygen evolution electrocatalysis on oxide surfaces." ChemCatChem 3.7 (2011): 1159-1165.

• The slopes of these scaling relations arerelated to the number of bonds to thesurface each intermediate partakes in.

Scaling relations limit the lowering of the overpotential for OER of planar catalysts beyond, say, 300 mV.

Relationship of overpotential for OER on

interlayer distance

40

Kang et al., Journal of the American Chemical Society (2017), 139(5), 1863-1870

Exfoliation

TBAOH

10

days

TBAOH

10

days

K+H2O

50 nm 100 nm

MnO2

43Kang et al., Journal of the American Chemical Society (2017), 139(5), 1863-1870

44

Overpotential is a strong function of interlayer distance

The larger the interlayer distance, the smaller the overpotential for the OER

Kang et al., Journal of the American Chemical Society (2017), 139(5), 1863-1870

SummaryTheory and Computation has helped guide the modification and explain the reactivity of layered electrocatalysts.

Placement of an already active OER catalyst in the interlayer region of a layered material can make the material even more active

• Results have a broad impact with regard to improving the catalytic activity of other layered materials

45 45452017 EFRC-Hub-CMS PI Meeting,

Acknowledgements

• Daniel Strongin – PI– Nuwan Attanayake– Qing Kang– Samantha Shumlas– Akila Chathuranga Thenuwara

• Jianwei Sun (SCAN) DFT• Rick Remsing (MD simulations)• Mike Klein• Michael Zdilla - PI

– Ian McKendry• Eric Borguet - PI

– Laszlo Frazer – Loranne Vernisse

46 4646 462017 EFRC-Hub-CMS PI Meeting,

XRD Analysis

47

Future Work

Build catalyst layer by layer

Theory will give us leads for effective 2D catalytic materials

48

Scientific Achievement Intercalating zero-valent copper into the van der Waals gap increases the water oxidation catalysis of birnessite by enhancing the interlayer charge transfer.

Significance and ImpactOut of plane conductivity governs electrocatalysis in layered materials. Our work proposes a novel method for enhancing out-of-plane conductivity in layered materials, thus improving catalysis.

Research Details– Zero valent copper can be incorporated into the interlayer region of

birnessite by a simple disproportionation reaction of Cu(I)-precursor.

– Electrocatalytic studies reveal that Cu modified birnessite possess improved water oxidation activity over pristine birnessite with lower Tafelslopes and overpotentials.

– Experimental and DFT calculations suggest that copper intercalation reduces the charge transfer resistance and enhances out-of -plane interlayer conductivity.

Turning a poor catalyst into an efficient catalyst-Copper

Intercalated Birnessite as a Water Oxidation Catalyst

Work was performed at Temple University

Akila Thenuwara, Samantha Shumlas, Nuwan Attanayake, Elizabeth Cerkez, Ian McKendry, Laszlo Frazer, Eric Borguet,Qing Kang, Michael Zdilla, Jianwei Sun, Daniel Strongin Langmuir (2015). DOI:10.1021/acs.langmuir.5b02936

Center for Computational Design

of Functional Layered Materials

Co substituted NiFe LDH by coprecipitation

XRD shows no changes in the interlayer space in Co substituted NiFe LDH upon various cobalt doping percentages.

Layered samples of Interest

MoS2

MnO2

51

52

Thrust III/Forum BExperimental characterization of

2D materials and applications

-Develop and understand 2D materials and howTo manipulate their properties for particular applications

-While there are many possible applications, one isWater splitting, both photochemically and electrochemically

-Test cases for validation of Theoretical and computationaldevelopments within center

MoS2

MnO2

Water Oxidation

2 H2O O2 + 2H2

2 H2O O2 + 4H+ + 4e-

2 H+ + 2 e- H2

1.23 V

Oxygen Evolving

Complex

Photosystem II

Photosynthesis

Cox, et.al. Science. 2014. 345. 6198. 804-808. M.M. Najafpour et al. Biochimica et Biophysica Acta, 2017. 1858, 156–174Blakemore JD, et.al. Chemical Reviews. 2015 Jul 7;115(23):12974-3005.

Mn(IV) and Mn(III)

Cu Intercalation

54

Reduction of Dimensionality

Bulk Birnessite (MnO2)

Nanosheets (2d) Birnessite (MnO2)

3D

2D

Benchmark

NovelMaterials?

Sun et al., Journal of Alloys and Compounds 2013, 569, 136

55

Oxygen evolution reaction(OER) on cobalt intercalated NiFe layered double hydroxides

(NiFe LDH)

Ni2+

Fe3+

Photosystem II

Birnessite

• Formed by precipitation in lakes, oceans and groundwater

– Manganese nodules

• Structure

• K0.20-0.018Mn(IV0.59III0.26II0.13) O1.66 ● nH2O

• Na0.58Mn(IV1.42III0.58) O2 ● nH2O

• Ca, any other cation

58Lucht, et. al, J. Phys. Chem. C 2015, 119, 22838−22846“Manganese nodule”. J. Wikipedia.org

59efrc.cst.temple.edu

XRD Analysis


DFT

Cu introduces states in gapBand gap

Jianwei Sun - Temple

Effect of Cu in the interlayer region of birnessiteD

ensi

ty o

f st

ates

Energy (eV)

Den

sity

of

stat

es

Energy (eV)

MnO2 Cu/MnO2


Good catalyst, RuO2 slope is 59 mV

Cu intercalated Birnessite



Method adapated from J. P. Motter, K. J. Koski and Y. Cui, Chemistry of Materials, 2014, 26, 2313-2317.

2Cu(I) → Cu(0) + Cu(II)

Copper Intercalated

Birnessite

63

Thenuwara et al., Copper-Intercalated Birnessite as a Water Oxidation Catalyst, Langmuir, 2015, 31 (46), pp 12807–12813



Catalysis in the Interlayer EnvironmentSummary of OER activities

Catalyst K/Mn atomic ratio

Intercalated Ni at. %

TOF (s-1) at

η=0.40V

mass activity (A g-1) at η=0.40V

Tafel slope(mV

dec-1)Birnessite 0.17 0.00 0.0004 2.0 243±7

Ni2+/Birnessite (Ni 6.1%)

0.00 6.1 0.031 24 72±4


0.05 6.5 0.056 43 65±3


0.06 7.7 0.061 46 60±3

β-NiOH2 0.00 N/A 0.0036 2.5 105±4



High Mn(III)

This catalyst has a higher TON than any birnessite reported In the literature!

66 662017 EFRC-Hub-CMS PI Meeting,

Birnessite prepared decorated with Mn(III)Mn(II) + Mn(IV) →2Mn(III)k


McKendry et al. DECORATION OF THE LAYERED MANGANESE OXIDE BIRNESSITE WITH MN(II/III) GIVES A NEW WATER OXIDATION CATALYST WITH FIFTY-FOLD TURNOVER NUMBER ENHANCEMENT, Dalton Transactions 44 , 12981-12984 (2015)

Ce(IV) used as oxidant

Experimental Test

67

Polaronic defect states of Mn(III) is predicted to achieve energy resonance with conduction band minimum at a AOS of 0.125 fortwo parallel layers

Difference in AOS of surface and bulkExceed critical valueassociated with0K/2K



ThermodynamicThreshold for waterOxidation ; Eo=0.2Versus Ag/AgCl at pH 14

Quoted at10 mA/cm2

{[(1 ) / ] }[ ]

nF RT

oi i e

overpotentialO

2P

rod

uct

Electrocatalysis Measurement


MnO2

Cu-intercalatedSuib and coworkers, JACS, 136, 2014, 11452

Literature Values for MnO2


Overpotential is relatedto the reaction barrier,the-lower-the-better

theory and computation working with...

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