Supplementary Materials

Functionalized conjugated polymer nanofibers with plasmonic Au nanoalloy for photocatalytic hydrogen generation under visible-NIR

light irradiation

Srabanti Ghosha, Divya Rashmib, Susmita Beraa, Rajendra N. Basua

aFuel Cell and Battery Division, CSIR-Central Glass and Ceramic Research Institute, 196, Raja S. C. Mullick Road, Kolkata-700032, India,

bDepartment of Mechanical and Manufacturing Engineering, Manipal Institute of Technology, Karnataka

Email: ghosh.srabanti@gmail.com, rnbasu@cgcri.res.in

Figures related to characterization and application

XRD S8, S15XPS S9TEM and STEM images S10- S13 DRS S13LSV and IPCE S14Band diagram S15Photocatalytic H2 generation S15 Photocatalytic MO degradation S16-S17 Recycling test S18Cyclic voltammetry S18Effect of scavenger on photocatalysis S18Table S19-S21References S21

1

Fig.S1 XRD patterns for the synthesized Au/PPy, Pd/PPy, Pt/PPy, Au54Pd46/PPy,

Au50Pt24Pd26/PPy nanohybrid.

Fig.S2 (a) XPS spectra of Au50Pt24Pd26/PPy nanohybrid, magnified XPS spectra of (b) Au 4f, (c) Pt 4f, (d) Pd 3d in nanohybrids.

Fig.S3 (a,b) Pt/PPy nanohybrids, at two different magnifications, (c) HRTEM image. (d, e)

Pd/PPy nanohybrids at two different magnifications, (f) HRTEM image.

Fig.S4 Transmission electron micrograph of (a,b) Au54Pd46/PPy at two different magnifications,

(c) HRTEM of Au54Pd46/PPy.

Fig.S5 (a) HAADF-STEM image of Au50Pt24Pd26/PPy nanohybrids (b)-(d) HAADF-STEM-EDS

mapping images of Au50Pt24Pd26/PPy NHs.

Fig.S6 The Uv-Vis diffuse reflectance spectra (DRS) of PPy and nanohybrids.

Fig.S7 Linear sweep voltammetry (LSV) plot of PPy and Au50Pt24Pd26/PPy nanohybrids.

Fig.S8 IPCE of PPy and Au50Pt24Pd26/PPy nanohybrids.

Fig.S9 Band diagram of PPy and Au50Pt24Pd26/PPy nanohybrids based on Mott–Schottky analysis.

Fig.S10 (a) Photocatalytic hydrogen generation in presence of catalyst Pt/PPy, Pd/PPy, and

Au41Pd29Pt30/PPy NHs under visible light irradiation from an aqueous solution containing 25

volume % methanol at pH 7. (b) Effect of Au loading in nanohybrids for photocatalytic hydrogen

generation. (c) Hydrogen generation using Au/PPy NHs at varying the catalyst amount of 0.5

mg ml–1, 0.25 mg ml–1 and 0.125 mg ml–1 respectively. (d) Effect of pH on the photocatalytic

hydrogen generation using Au/PPy NHs as catalyst.

Fig.S11 XRD patterns of other carbon, graphene and carbon nanotubes supported gold nanoparticles.

Fig.S12 (a) MO degradation in presence of PPy and Au/PPy, Pd/PPy, Pt/PPy, Au50Pt24Pd26/PPy

NHs under visible light using 0.5 mg ml–1 of catalysts and (b) Comparative apparent rate

constant (k-values) of the NHs for the photocatalytic MO degradation. (c) NIR light irradiation.

Light source using 300 W Xe lamp with a UV light cut off filter (420 nm).

2

Fig. S13 (a) Photocatalytic MO degradation in presence of catalysts PPy and Au/PPy, Pd/PPy,

Pt/PPy, Au50Pt24pd26/PPy NHs under UV light irradiation. (b) Comparative apparent rate constant

(k-values) of the nanocomposites for the photocatalytic MO degradation.

Fig. S14 (a) Photocatalytic MO degradation in presence of catalysts Au/PPy, Au/PEDOT and

Au/PANI NHs under visible light irradiation. (b) Comparative apparent rate constant (k-values)

of the nanocomposites for the photocatalytic MO degradation.

Fig.S15 Cyclic Voltammetry of PPy recorded at scan rate of 20 mV/s in acetonitrile and 0.1 M

tetrabutylammonium perchlorate. Ferrocenium/ ferrocene (Fc/Fc+) redox potential has been

measured to calibrate the pseudo reference electrode (0.241 V νs. Ag). The energetic levels of

PPy are obtained by the following equation: EHOMO (eV) = (4.8 + Eox_onset 0.241) and ELOMO (eV)

= (4.8 + Ered_onset 0.241).

Fig.S16 Photocatalytic degradation of MO by Au/PPy NHs with different scavengers (10−4 mol

L−1 of Cu and 2-propanol) under both visible and near infrared light irradiation.

Table:

Table S1 Quantification of metal loading on polymer nanofibers by using ICP-AES techniques.

Table S2 Electrochemical parameters calculated from Mott–Schottky plot for PPy and

Au50Pt24Pd26/PPy electrodes.

Table S3 Comparison of photocatalytic performance of nanohybrids for hydrogen generation.

Mechanism of formation of nanohybrid

3

Indeed, radiolysis is a powerful method to synthesize nanoparticles of controlled size and shape

in solutions as well as in heterogeneous media and no chemical reactants is needed to reduce the

metal. The radiolytic formation of gold atoms is followed by association of the atoms with ions

and complexes, dimerization reduction reactions, and coalescence of the resulting oligomers,

leading to Au nanostructures. A similar mechanism is possible for the other metals, viz., Pt or Pd

nanoparticles. Monometallic clusters are formed initially; a further association and reduction

reaction gradually builds the bimetallic or trimetallic alloyed clusters. The formation of the

alloyed structures or the segregation of metals in the core–shell type structures probably depends

on the kinetic competition between the irreversible release of metal ions, which are displaced by

excess noble metal ions after electron transfer, as well as radiation-induced reduction of both

metal ions.

Metal ions can be reduced by solvated electrons (e-sol) and 2-propanol radicals (CH3)2–C.OH produced by the solvent radiolysis.

(CH3)2CHOH e-sol; solvated protons ((CH3)2CHOH2+), (CH3)2C.OH and other

radiolytic products.

(CH3)2CHOH + OH•(H•) (CH3)2C•OH + H2O (4)

e-sol + M+ M0 M=Au, Pt, Pd (5)

(CH3)2C•OH + M+ (CH3)2CO + M0 (6)

AuIII +e-solAuI (7)

AuIII + (CH3)2C•OH AuI + (CH3)2CO (8)

2AuI Au0 + AuII (9)

nAu0 (Au)n (10)

The diffraction peaks as shown in Fig. S1a can be indexed as the (111), (200), (220), (311) and

(222) corresponds to the face-centered cubic (fcc) structure of Au (JCPDS 04-0784). The strong

peaks at 2θ values of 39.65, 46.1, 67.5, 81.1, and 86.1 correspond to the (111), (200), (220),

(311), and (222) faces of Pt crystal, respectively. The diffraction peaks are present at 2θ = 40.6 ,

46.6, 68.4, 82 and 87 which can be indexed as the (111), (200), (220), (311) and (222) facets

diffractions of face-centered cubic (fcc) Pd (JCPDS No 05-0681), respectively. The angle shift in

the diffraction peaks indicates a lattice parameter change due to alloy formation between the

4

metallic phases. As Pt, Pd and Au have similar lattice parameters and cubic structures, the

diffraction peaks of the resulting PtPdAu alloys are similar to those of pure Pt, Pd, and Au. A

broad feature of peak centered ~ 24.8°, which can be assigned to the repeat unit of pyrrole ring,

implying an amorphous polymer structure.

30 40 50 60 70 80 90

(222)(311)(220)(200)

(111)

2

Pt/PPy

Inte

nsity

/Cou

nts

Pd/PPy

Au54Pd46/PPy

Au50Pt24Pd26/PPy

Au/PPy

Fig.S1 XRD patterns for the synthesized Au/PPy, Pd/PPy, Pt/PPy, Au54Pd46/PPy, Au50Pt24Pd26/PPy nanohybrid.

X-ray photon spectroscopy (XPS) was carried out further to elucidate the chemical compositions

trimetallic nanohybrids of Au, Pd and Pt. The presence of strong XPS signals at 196.5, 285.5,

401.5, and 532 eV in the survey spectrum of both Ppy and Au50Pt24Pd26/PPy nanohybrid which

correspond to Cl 2p, C 1s, N 1s, and O 1s, respectively (Fig.S2), indicating the chemical

environment of Cl, C, N, and O originated from Ppy. Other strong XPS signals at 70.0, 84.1 and

346.2, eV correspond to Pt 4f, Au 4f, and Pd3d respectively in the survey spectrum.

Au41Pd30Pt29/PPy supports the formation of trimetallic composition.

5

0 200 400 600 800 1000

Ppy Nanofibers Au50Pt24Pd26/Ppy

Cl2p

Au

4d

Pt 4

f

Binding Energy/eV

Inte

nsity

/cou

nts

C 1

s

Au

4f

Pd 3

dN

1s

O 1

s

(a) (b)

(c)

70 72 74 76 78

Peak Analysis

4f7/2

4f5/2

Inte

nsity

/Cou

nts

Binding Energy/ eV

Pt 4f

Adj. R-Square=9.92191E-001 # of Data Points=92.

Degree of Freedom=92.SS=1.67056E+003

Chi^2=2.08820E+001

Date:4/10/2017Data Set:[Au4f]Sheet1!B

Fitting Results

Max Height162.9526865.0241495.4521768.14853

Area IntgP28.2255114.9416319.6325337.20033

FWHM1.094511.451611.299313.5

Center Grvty70.5976771.6510473.9274.85101

Area Intg189.80006100.47372132.01728250.15047

Peak TypeGaussianGaussianGaussianGaussian

Peak Index1.2.3.4.

82 84 86 88 90 Binding Energy/eV

4f5/2

In

tens

ity/c

ount

s

Peak Analysis

4f7/2 Au 4f

Baseline:ExpDec1

Adj. R-Square=9.83711E-001 # of Data Points=82.

Degree of Freedom=78.SS=1.51062E+004

Chi^2=1.93669E+002

Date:4/10/2017Data Set:[Book2]Sheet1!B

Fitting Results

Max Height381.00969280.43866

Area IntgP57.1318742.86813

FWHM0.789140.80446

Center Grvty83.38887.088

Area Intg320.04851240.14414

Peak TypeGaussianGaussian

Peak Index1.2.

334 336 338 340 342 344 346

Peak Analysis

Inte

nsity

/Cou

nts

Binding Energy/eV

3d5/2

3d3/2

Pd 3d

Baseline:ExpDec1

Adj. R-Square=9.97216E-001 # of Data Points=130.

Degree of Freedom=117.SS=3.40434E+004

Chi^2=2.90970E+002

Date:4/10/2017Data Set:[Book6]Sheet1!B

Fitting Results

Max Height1094.69639712.04701296.33291221.08635

Area IntgP36.2749524.1787722.2291317.31715

FWHM1.106391.133752.508752.61532

Center Grvty335.01021340.30193336.16796341.60171

Area Intg1289.22698859.32383790.03267615.4588

Peak TypeGaussianGaussianGaussianGaussian

Peak Index1.2.3.4.

(d)

Fig.S2 a) XPS spectra of Au50Pt24Pd26/PPy nanohybrid, magnified XPS spectra of (b) Au 4f, (c) Pt 4f, (d) Pd 3d in nanohybrids.

Fig.S2 (b), (c) and (d) illustrate the XPS spectra of Pd 3d, Pt 4f and Au 4f, regions. The core-

level Pd 3d spectra display a doublet signal with binding energies of 335.3 and 340.4 eV for Pd

3d5/2 and Pd 3d3/2, respectively, corresponding to the Pd signal. Another small doublet around

336.7 and 342.1 can be assigned to the Pd 3d3/2 and Pd 3d5/2 peaks of PdO (Fig.S2b).The signals

located at 70.6 and 74.08eV could be assigned to the binding energies of Pt 4f7/2 and Pt 4f5/2 of

metallic Pt0, respectively (Fig.S2c). The peak at 83.4 and 87.1 eV in binding energy scale,

respectively observed from Au 4f7/2 and Au 4f5/2 spin-orbit doublets correspond to a metallic-gold

(Au0) which are well consistent with those observed in Au NPs (Fig.S2d).

The homogeneous distribution of extremely fine Pt NPs supported on the surface of the PPy

nanofibers is evident from the TEM images (Fig.3a, b). The average particle size of Pt NPs is

6

found to be 3.5 nm as can be measured from the TEM bright-field image. The HRTEM image of

Pt/PPy is shown in Fig.3c, indicating that the inter-planar distance between the fringes of Pt NPs

about 0.234 nm which is consistent with the spacing of (111) planes.

0.234 nmPt (111)

2 nm

c

d200 nm 50 nm

b

b0.22 nmPd (111)

5 nm50 nm100 nm

ed f

a

Fig.S3 (a,b) Pt/PPy nanohybrids, at two different magnifications, (c) HRTEM image. (d, e) Pd/PPy

nanohybrids, at two different magnifications, (f) HRTEM image.

The size distribution of pure Pd NPs estimated from the TEM bright-field image (considering

representative number>300 isolated particles) and the average diameter (D) of Pd NPs is 4.7 nm

as shown in Fig. 3(d, e). The HRTEM image shows the characteristic lattice fringes of Pd NPs

in the surrounding of PPy matrix (Fig.3f). The inter-planar distance in the lattice fringes is

measured to be 0.22 nm, which corresponds to the (111) planes of metallic Pd.

Another bimetallic composition, Pd54Au46/PPy nanoalloys were also formed on the polymer

nanofibers by radiolytic technique and homogeneous distribution and crystallinity shown in

TEM and HRTEM images (Fig. S4a-c). The presence of Au and Pd in the nanoalloys has been

determined using EDX analysis.

7

0 5 10 15 20 250

200

400

600

800

1000

1200

1400

1600

1800 EDS of Au54Pd46/Ppy

PdCu

Inte

nsity

/ a.u

.

Energy/KeV

C

PdAu

ClCu

Pd

Au

Cu

5nm0.2 m

(a) (b)

(c)

Fig.S4 Transmission electron micrograph of (a,b) Au54Pd46/PPy NHs at two different magnifications, (c)

HRTEM of Au54Pd46/PPy NHs.

The TEM bright-field images as well as the STEM-HAADF images of Au50Pt24Pd26/PPy show

the presence of nanoparticles (NPs) of different sizes (ranging from <10 nm to ~250 nm) adhered

to the polymer nanofibers (Fig.S5). The maps also suggest that Pd NPs are finer (~10 nm) in

general, and in cases of small Au-containing NPs, Au has formed a shell on these fine Pd-NPs as

indicated by the large size in Au-map and smaller sizes in Pd-map for several NPs, as indicated

by arrowheads. The elemental maps also suggest that Pt form better alloys with Au rather than

Pd. Both Pd and Pt tend to retain their tiny sizes (i.e., ~10 nm).

8

Fig.S5 (a) HAADF-STEM image of Au50Pt24Pd26/PPy nanohybrids (b)-(d) HAADF-STEM-EDS mapping images of Au50Pt24Pd26/PPy.

Fig.S6 The UV-Vis diffuse reflectance spectra of PPy and nanohybrids.

9

200 300 400 500 600 700 800

20

30

40

50

60

70

80

90

100 PPy Au/PPy Pd/PPy Pt/PPy

Au50

Pt24

Pd26

/PPy

Ref

lect

ion

/ %

Wavelength / nm

0.4 0.6 0.8 1.00.0

1.5

3.0

4.5

6.0

7.5 PPy-dark PPy-light Au50Pt24Pd26/PPy-dark Au50Pt24Pd26/PPy-light

Potential V vs Ag/AgCl

j /m

A c

m-2

Fig.S7 Linear sweep voltammetry (LSV) plot of PPy and Au50Pt24Pd26/PPy nanohybrids.

Fig.S8 IPCE of PPy and Au50Pt24Pd26/PPy nanohybrids.

10

0.4 0.6 0.8 1.00.0

1.5

3.0

4.5

6.0

7.5 PPy-dark PPy-light Au50Pt24Pd26/PPy-dark Au50Pt24Pd26/PPy-light

Potential V vs Ag/AgCl

j /m

A c

m-2

300 350 400 450 500 550 600 650 700 7500.00

0.05

0.10

0.15

0.20

0.25

0.30

0.35

0.40

PPy Au50Pt24Pd26/PPy

% IP

CE

Wavelength/ nm

-1

0

1VB

0V, H2/H+

1.23V, O2/H2OVB

CBCB

PPy Au50Pt24Pd26/PPy

e– e–

h+ h+

e– e–

h+ h+

Fig.S9 Band diagram of PPy and Au50Pt24Pd26/PPy nanohybrids based on Mott–Schottky analysis.

7

15

12

9

0

3

6

9

12

15

13

Am

ount

of H

2/ m

mol

h-1

pH4 7 10

0 20 40 600

5

10

15

20

25

Time / min

Pt/PPy Pd/PPy Au41Pd29Pt30/PPy

Am

ount

of H

2/ m

mol

h-1

6

8

10

12

14

16

12

6

3

1

Am

ount

of H

2/ m

mol

h-1

Au loading (%)

a b

0 20 40 60 800

4

8

12

16

20 0.5 mg ml-1

0.25 mg ml-1

0.12 mg ml-1

Am

ount

of H

2/ m

mol

h-1

Time / min

c d

Fig.S10 (a) Photocatalytic hydrogen generation in presence of catalyst Pt/PPy, Pd/PPy, and

Au41Pd29Pt30/PPy NHs under visible light irradiation from an aqueous solution containing 25 volume %

methanol and 0.5 mg ml–1 of catalysts at pH 7. (b) Effect of Au loading in nanohybrids for photocatalytic

hydrogen generation. (c) Hydrogen generation using Au/PPy NHs at varying the catalyst amount of 0.5

mg ml–1, 0.25 mg ml–1 and 0.125 mg ml–1 respectively at pH 7. (d) Effect of pH on the photocatalytic

hydrogen generation using Au/PPy NHs as catalyst using aqueous solution containing 25 volume %

methanol and 0.5 mg ml–1 of catalysts.

11

Supporting data

20 30 40 50 60 70 80 90In

tens

ity /C

ount

s2/

Au/PANI Au/CNT Au/rGO Au/PEDOT

Fig.S11 XRD patterns of other carbon supported gold nanoparticles.

0 45 90 135 180 2250.0

0.2

0.4

0.6

0.8

1.0

Time/min

C/C

0

PPy Au/PPy Pt/PPy Pd/PPy Au50Pt24Pd26/PPy

0 20 40 60 80 100 1200.0

0.2

0.4

0.6

0.8

1.0 PPy Au/PPy Au50Pt24Pd26/PPy

Time/min

C/C

0

VIS

NIR

ba

0.005

1 2 3 4 50.00

0.01

0.02

0.03 1. PPy2. Au/PPy3. Pt/PPy4. Pd/PPy 5. Au50Pt24Pd26/PPy

Apa

rent

k v

alue

c

Fig.S12 MO degradation in presence of PPy and Au/PPy, Pd/PPy, Pt/PPy, Au50Pt24Pd26/PPy NHs under

visible light using 0.5 mg ml–1 of catalysts and (b) Comparative apparent rate constant (k-values) of the

NHs for the photocatalytic MO degradation. (c) NIR light irradiation. Light source using 300 W Xe lamp

with a UV light cut off filter (420 nm).

12

The calculated rate constant order is as follows, Au50Pt24Pd26/PPy Au/PPy Pd/PPy Pt/PPy PPy. Fig.S12c illustrates a unique example of polymer and hybrid based photocatalyst, which illustrates excellent photocatalytic performance under near infrared light (λ>700 nm). This result indicates that the presence of infrared-absorptive CP can definitely enhance the utilization of solar energy.

0.005

0.017

0.009

0.004

0.04

1 2 3 4 50.00

0.01

0.02

0.03

0.04 1. PPy2. Au/PPy3. Pt/PPy4. Pd/PPy5. Au50Pt24Pd26/PPy

Apa

rent

k v

alue

0 30 60 90 120 150 1800.0

0.2

0.4

0.6

0.8

1.0

Time/min

C/C

0

PPy Au/PPy Pd/PPy Pt/PPy Au50Pt24Pd26/PPy

a b

Fig. S13 (a) Photocatalytic MO degradation in presence of catalysts PPy, Au/PPy, Pd/PPy, Pt/PPy, and Au50Pt24Pd26/PPy under UV light irradiation using 0.5 mg ml–1 of catalysts. (b) Comparative apparent rate constant (k-values) of the nanohybrids for the photocatalytic MO degradation.

0 50 100 150 200 2500.0

0.2

0.4

0.6

0.8

1.0

Time/min

C/C

0

Au/PPy Au/PEDOT Au/PANI

0.1

0.13

0.16

1 2 3

1. Au/PPy2. Au/PEDOT3. Au/PANI

Apa

rent

k v

alue

a b

Fig. S14 (a) Photocatalytic MO degradation in presence of catalysts Au/PPy, Au/PEDOT and Au/PANI under visible light irradiation using 0.5 mg ml–1 of catalysts. (b) Comparative apparent rate constant (k-values) of the nanocomposites for the photocatalytic MO degradation.

13

Supporting data

-1.0 -0.5 0.0 0.5 1.0 1.5 2.0 2.5

-0.06

-0.04

-0.02

0.00

0.02

0.04

0.06

I/mA

Potential/V (vs Ag)

Fig.S15 Cyclic Voltammetry of PPy recorded in acetonitrile and 0.1 M tetrabutylammonium perchlorate

at scan rate of 20 mV/s. Ferrocenium/ ferrocene (Fc/Fc+) redox potential has been measured to calibrate

the pseudo reference electrode (0.241 V νs. Ag). The energetic levels of PPy are obtained by the

following equation: EHOMO (eV) = (4.8 + Eox_onset 0.241) and ELOMO (eV) = (4.8 + Ered_onset 0.241).

Fig.S16 Photocatalytic degradation of MO by Au/PPy NHs with different scavengers (10−4 mol L−1 of Cu

2-propanol and triethanolamine) under both visible and near infrared light irradiation.

14

0

20

40

60

80

100

TEOAPropanol

VIS NIR

Deg

rada

tion

of M

O (%

)

O 2Argon

Cu2+

Table S1 Quantification of metal loading on polymer nanofibers by using ICP-AES techniques.

Metal loaded on PPy

ICP-AES

Pd-Pt-AuAtomic content (at.%)

Actual metal loading (wt.

%)Pd Pt AuPt 100 - 162

Pd 100 - - 201

Au - - 100 162

PdAu 54 - 46 263

PtPdAu 26 24 50 202

Table S2 Electrochemical parameters calculated from Mott–Schottky plot for PPy and Au50Pt24Pd26/PPy

electrodes.

Catalyst Efb

in Vvs Ag/AgCl

ECB

in V vs RHE

EVB

in V vs RHE

Eg

in eVNA

in cm-3

PPy 0.29V -0.96 0.9 1.84 1.431011

Au50Pt24Pd26/PPy 0.35 -0.86 0.96 1.8 7.931011

Table S3 Comparison of photocatalytic performance of nanohybrids for the hydrogen generation.

Catalyst Light Source Sacrificial Agent

Amount of H2

μmolH2

generation rate

μmol g-1h-1

Reference

Au/TiO2 Visible light, 2h _ 1376 ± 60 _ 38

Pt/TiO2-Au 300 W xenon arc lamp

Water/methanol

mixture (9:1 V/V)

20 _ 39

Au/g-C3N4

Au/g-C

visible-light, λ>400 nm

10 vol% of TEOA

532.2 _ 40

15

3N4

Au/g-C3N4

Ag/g-C3N4

Porous nanofiber

300 W Xe lamp, >420 nm, 4h

TEOA, 10 mL 125 _ 41

CdS /Au /g-C3N4

xenon lamp with UV cut off filter,

λ > 420 nm

20 volume % methanol

_ 19.02 42

Au/TiO2–g-C3N4

150 W Hg lamp, 5h

methanol or TEOA10 vol

%

2200 _ 43

Pt–Co/g-C3N4 visible light (>420 nm)

_ _ 12 44

Carbon Quantum Dot/g-

C3N4

visible light, λ > 420 nm,5h

TEOA solution

and Pt as a co-catalyst

17590.0 3538.3  45

Crystalline g-C3N4

visible light irradiation, λ >

420

3 wt% Pt as a co-catalyst and

TEOA

_ 204 46

conjugated polymers based perylenediimide

visible light irradiation, λ >

420

Water/Methanol/

TEOA solution (1:1:1 volume ratio)

_ 7.2 47

Planarized Conjugated

Polymer

300-W Xe lamp, λ > 420 nm, 5h

Methanol/TEOA

solution

_ 92 48

g-C3N4 150-W Xe lamp, λ > 400 nm,

triethylamine/water mixture(4.0 mL, 2/8,

v/v)

_ 106.9 49

Pt/g-C3N4 1000W xenon lamp with an UV (420 nm) cut-off

filter

10 vol.% TEOA as an

electron donor

_ 149 50

Pt/g-C3N4 300 W Xe lamp, λ > 420 nm

10 vol.% TEOA and 3 wt. % Pt as a

cocatalyst

_ 750 51

Pt@TiO2 150 W Xe lamp, λ > 420 nm

0.90 mol L-1

TGA as sacrificial

agent

_ 61.8 52

PtNi/g-C3N4 300 W Xe lamp, λ > 420 nm

10 vol.% TEOA

500 104.7 53

Au/PPy

Au50Pt24Pd26/PPy

250-W Xe lamp, λ > 420 nm,

75 min

25 volume% methanol

2560

6970

15000

40000

Present Study

16

17