445

PROSPECTIVE USAGE OF PHOTOELECTROCHEMISTRY FOR ENVIRONMENTAL CONTROL

S.K. Haram and K.S.V. Santhanam

Chemical Physics Group, Tata Institute of Fundamental Research, Colaba Bombay 400 005, India

1.

INTRODUCTION:
Solar energy has been playing a vital role in maintaining a

cleaner environment ever since this universe was formed. The photosynthesis s occurring in green plants has been converting COz into useful which i products; however, the warming due to an deforestation during the last two decades has and the green house caused an alarm as the process of C02 removal has been reduced. A global increasing concentration of CO
2

effect are of considerable concern in todays environment. The ideal control of the concentration of C02 in the atmosphere would be to convert

it a t the point of its entry into the atmosphere. If we examine todays

input to this toxic waste (C02 is less toxic than CO; toxicity level of CO = 5000 ppm, toxicity level of CO= 50 ppm) it arises from industrial 2 wastes and automobile exhausts. The decontamination of this can be brought about by mimicing the photosynthetic process in a modified form i.e., utilising the photons of the sun in an appropriate manner to convert CO 2 into useful or less toxic waste. Among other toxic wastes entering into our atmosphere are H S, N 0, NO, HCN, hydrocarbons etc.. 2 2 Photoelectrochemistry can play a significant role in creating a cleaner environment by converting the above chemicals into other value added products. Although this concept has been in discussion in the
s slowly building up in recent last two decades, the practicality of it i

times as a result of
semiconductor/electrolyte

a large number of fundamental studies at the

interface. Several oxidative and reductive

processes have been brought out in the last several years (1-10) at the semiconductor electrodes. An excellent review ( 1 ) on photoelectrochemical oxidation processes summarises the developments in this area. The present review discusses the photoelectrochemical reductive processes that have

446

been carried out at the semiconductor electrodes which have a bearing on the environmental control by the polluting gases.

2 .

PHOTOELECTROCHEMICAL REDUCTION OF C02

a)

At bare semiconductors:
The semiconductors which are suitable for photoelectrochemical

reduction of C02 are shown in Figure 1.

-'T
w I
v,

ui

>
+2

>

--

CdS

AlAs

Eo= -0.096V CO*/CH30H

Lo= -0.16V C02/HCH0

+3 --

co,/co

EO=

-0.1 1 v

Figure 1. Band diagram of selected semiconductors for C02 reduction

A wide selection of semiconductors i s capable of effecting this reduction.

Out of these several semiconductors, atleast three of them have been examined in detail. p-GaAs single crystal electrode has been used by Zafrir et a1 (11). The photocurrent onset potential for CO was observed at +O.O5V 2 in 3.1 M CaC12 containing 0.87 M HC1 and 0.07 M V ( I I ) chloride. The

V(II)/V(III)

couple

w a s

used

to

bring

about

efficient

electron

transfer reaction at the semiconductor electrode. A faradaic yield of 1.2% for HCOOH has been obtained at a potential of -0.7V at a current density of 8 . 5 mWcm
2

The optical to chemical energy conversion efficiency is

447
estimated at 0 . 2 % . The other products have the following faradaic yields; HCHO = 0.3% and CH OH = 0.13%.The following step wise conversion of C02 is
3

proposed at the semiconductor electrode.

co2
COO-'

+
+

>

COO-'

(1)

H +
->

> HCOO'
HCOO

(2)

HCOO'+ e

(3)

This conversion produces H2 as the bye product through direct reduction of H+. The p-CdTe and p-InP electrodes have also been investigated ( 1 2 ) ; while the reaction scheme is essentially as indicated above, the net formation of formic acid is demonstrated to be a function of the pH of the medium. Hence using the solutions of supporting electrolytes such as carbonates, sulphates, phosphates and perchlorates of alkali salts or tetra alkyl ammonium salts, the reaction ( 4 ) has been effected.

co-'+ 2

H ~ O + e >

HCOO-+ OH-

(4)

The possibility of adsorbed C O ', indicated C02+ e

playing a role in the photoelectrochemical

conversion at p-CdTe has been reported (13). The following steps are

7 c o , .
5

(5)

co2 ' + co2--

o=c-0-co-0-

(6)

O=C-0-CO-O-+ e

> o=c-o-co-6
>

(7)

o=c-0-co-0-

coz- + co

(8)

This mechanism has been invoked to account for the different products obtained at different electrodes such as Pb and p-CdTe. Table 1 summarises the conversion efficiencies of CO conversion of CO
s to HCOOH i
2

a t the semiconductor electrodes. It is

reached, while at p-CdTe in the same obtained. A lso the conversion of

interesting to note that at p-GaP in Na2C03 electrolyte, a very high

2

electrolyte a very low conversion i s

448

C02 to CO i s efficient

at p-CdTe in non-aqueous electrolyte. The

conversion of C02 to CH OH i s very high at p-GaAs at a neutral pH. While no 3 s possible on the basis of the band diagram, it appears rationalisation i some specific adsorption of the electrolyte and C02 might be playing a role in the conversion.

Table

1:

Photoelectrochemical electrodes.

reduction of

C02

a t

semiconductor

Semiconductor

Incident power mW/cm

2

Medium Bias Applied

Faradaic yield
1
2

Effi Ref c i ency

/o

D-GaAs

980

0.32 M -0.50 0.032 0.0180.007 VClz in 4 M HC1 -0.65 (8.4hours)

0.07 M

0.045

11

90

0.012 0.003 0.0013 -

0. 1 0

11

VC12 in 4 M HC1 p-GaAs

0.5

-1.05 0.07

0.003

1 la

KC 1 p-GaAs

Na2S04
H2

-1.15

0.1 to 0.8

llb

p-CdTe

0.1 M

-1.6

15

TBAP in DMF
0.1M NH4C104

p-CdTe

3.2

0.1

M TBAF in
CH3CN
0.1 M

13

p-CdTe

0.8

-1.20 0.48

0.066

12

449
Table 1 ( c o n t d ) Na2C03

p-CdTe

0.8

0.1 M TEAP

-1.20

0.20

0.65

12

0.1 M TEABr
0.1

-1.20

0.076

0.78

TEACl
p-CdTe

-1.20

0.088

0.51

0.1 M TBAP H20/DMF 0.5 M Na2C03

-1.35

0.78

1Id

p-GaP

-0.75

0.78

0.024 0.005 -

lla

p-GaP

R4N'C10;
H2

-1.00

0.12

0.03

llc

p-InP

0.1 M TEAP
0.1 M

-1.20

0.36

0.08

0.26

12

TEABr
0.1 M TEAC 1 0.1 M Na2C03
0.1 M Na2S04

-1.20

0.28

0.31

-1.20 -1.20

0.31 0.17

0.28

-1.20

0.04

0.16

0.1 M Na3P04

-1.20

0.023

0.10

p-si

0.1 M LiC104

-0.75

0.63

17

CH CN/H20 3

The numbers i n t h e t a b l e header r e p r e s e n t s : 1.HCOOH 2.HCHO

3. CH30H

4. CO

450
The photoelectrochemical semiconductor H2 yield the in appreciable amounts (14);
of

reduction

C02

at

electrodes also produces H2

depends on the nature of the semiconductor surface. The mediation

of

photoelectrochemical

reduction

of

CO,

by

ammonium ions has been reported by Bockris et a1 (15). The first step in this mediation is the reduction of NH; and follows sequences ( 9 ) through

0.S niAcm-'

I
I

-0 5

-1.0

-1.5

1 -20 -2.5

wv vs SCE
Figure 2 . Current-voltage curves in DMF containing 5% H20 containing NH4C104in C02 A. 0.1 M NH C104 (in Ar atmosphere). B. 0.1 M atm~sphere,~C. 0.1 M TBAP (in Ar atmosphere). Taken from reference (15).

45 1

The current efficiency for CO formation in the presence of NH C10 depends 4 4 on the water content. Figure 2 shows the current-potential curves at p-CdTe electrode in DMF in the presence of NH4C104.

It is interesting to note

that the onset of photocurrent is substantially shifted to a negative potential in the presence of 0 . 1 M TBAP. The ammonium ion mediated reduction
i s obvious in the current-voltage curves.

b)

Semiconductors with deposited Catalysts: Several semiconductors coated with catalysts have been

investigated (14-18)for increasing the efficiency. At a metal coated p-GaP (14) the faradaic efficiency for C02 reduction i s about 50% in propylene carbonate containing tetra alkyl ammonium salt; in comparison the aqueous medium produced a faradaic yield of a few percent. The products in non-aqueous solvents are (COOH)2, HCOOH, CO and H2, The earliest attempt to catalyse the C02 reduction at
p-Si

was

carried

out

by

using this

tetra-aza-macrocyclic complexes of Co(I1) or Ni(II1

(17,191. At

modified semiconductor, the catalysed electrochemical reduction of CO 2 to CO occurs a t -0.55 V vs. SHE; the photoelectrolytic reduction produces H
2

2 about the reduction of C02 to CO in 100% faradaic yield. However, poisoning

of the semiconductor surface by either carbon or CO

besides CO in the ratio of CO/H

of 2:l. The modified electrodes can bring

has been postulated

for the decreasing efficiency with time. Table 2. The photoelectrochemical reduction of CO semiconductors SerniIncident Medium conductor power Wcm p-CaP
1.7
2

at a metal coated

Bias
voltage vs.Ag/ AgC 1

Faradaic yield ( % I
1
2.6

Efficiency
%

Ref

2
-

4
-

(uncoated)

0.1 M TEAP PC

-1.W

2.6 65

1 4

p-GaP/Au

1.7

0.1 M TEAP PC

-1.2v

94 trace

108

14

452

Table 2 (contd) p-GaP/In 1.7

0.1 M TEAP PC 0.1 M TEAP PC

-1.2

7 107 trace 121

14

p-GaP/Zn

1.7

-1.5

8 1 0 0 trace 1 0 9

1 4

p-GaP/Pb

1.7

0.1M TEAP PC 0.1 M NaC1O4 0.1 M NaC lo4

0.1 M KC104

-1.2

38

11 4 1 trace

90

14

p-GaP/ 2+ Ni(cyclam1 p-GaP/ 2+ Ni(cyclam1

2+ p-GaAs/ Ni(cyclam1

-0.2

83 1 6

1 6

-0.75

3 85

1 6

-0.95

- 47

3 0

1 6

H 2
p-Si/Tetra azo macro cyclic complexes of Ni

0.1 M LiC104

-0.75

- 63

32

1 7

CH3CN/H20

The numbers in the table header represents

1. (COOH)2 2.HCOOH 3.CO 4.H2

Faradaic efficiency

Bockris et a 1 (20a) proposed a model for photoelectrocatalysis

at metallised semiconductors.

3.

PHOTOCATALYTIC REDUCTION OF C02

The use
of

photocatalytic

semiconducting powders

for

effectively converting C02 into one organic such as HCOOH or HCHO or CH30H or CH3CH0 or C H OH has been carried out by a large number of investigators 25 (21-25). Ulman et a1 (21,221have used SrTi03 or Ti02 powders for effecting

453

the above conversion. At Sic the reduction of C02 proceeds to yield CH3CH0 and C H OH (23); by metallising SIC the photocatalytic reduction follows a 25 different route as shown in Table 3.

Table 3. Photocatalytic reduction of GO at semiconductors

2

Semiconductor

Metal mol%

HCOOH HCHO CH30H

p~
p~ p~

CH CHO EtOH Effici pil p~ ency

%

Refer ence

SiC/Pb SiC/Pd SiC/Pd SiC/Fe SiC/Fe SiC/Pt

0.44

1.2

1.1

0.20

0.018

4.4
9.8

24
24

0.011

1.6

1.3
1.6

1.6

0.014
0.14

0.020 2 . 0
0.80 1.6

1.3

10.0

24

0.95 1 . 1

6.8

24 24

1.03
0.30

2.3
2.1

0.86 1.5
1.2

0.05

11.0
8.0 5.8

1.1

0.03
0.016

24

si c/cu
sic/cu

0.25

1.5

0.90 0.78
0.74 0 . 6 5 0.40 0.50

24

0.93

1.3
1.9

4.8

24

sic

4.2

24

Heat of combustion of products

Eff lciency
The

Incident 1 ight energy of methanol and ethanol

100

formation

is

considered

through

photoexcitation of Sic powder and HCHO formed in the reaction. For example,
s sequenced as the ethanol formation i

HCHO +

HCHO

>CHO-CHO

+ 2

H+ + 2 e (13)

454

CHO-CHO + 2 H++ 2e > CH~CHO + 2 H++ 2 e

CH3CHO + 1/202
C~H~OH

(14)

(15)

where the electron i s contributed by the photoexcited Sic powder; H+ i s supplied by H20 via. the oxidation by Sic.

4.

PHOTOELECTROCHEMICAL DECOMPOSITION OF H2S

The photoelectrochemical conversion of H S to H
2

was reported by

1 (83). Kalyanasundaram and Gratzel (26a1, Crzyll et a1 (26b) and Chun et a Kalyanasundaram and Gratzel carried out the conversion of H S to H2
2

efficiently with CdS loaded with 0 . 5 % Ru02 a t a quantum efficiency of 35%

Chun et a1 conducted the photoelectrolysis of aqueous sulphide at n-Si coated with polypyrrole films and then loaded it with Ru02. The following 2sequence of reactions is postulated for the decomposition of S n-Si +hv > -

2 H++ 2e

h++ e

(16)

H~

(17)

The photocorrosion of the semiconductor has been reduced by the polymer coating. The simultaneous generation of H2 is an advantage of this process. This method gives a power conversion efficiency of 0.6% and a quantum efficiency of nearly 1%.

5.

PHOTOELECTROCHEMICAL CONVERSION OF SO2

The photoassisted reduction of SO a t p-WS2, p-Si and p-InP has 2 1 (27). The light assisted reduction been reported by Calabrese et a produces S20z- via. the reaction SO2
+

SO2

+ 2e

>

s20y

(19)

455

The current efficiency for this conversion is reported to be >90% at all the electrodes; the naked semiconductors such as p-InP show sluggish kinetics and hence requires metallisation. Figure 3 shows current-voltage curves for SO2 reduction at these semiconductor electrodes. At p-InP modified by Pt, a power saving efficiency of

I
Illuminated

'
Pt

05

b)-lmMS02 [o-Euq N] C 104 / CH,CN 100m V/s

Illuminated R
Q -1nP (naked)

n (platinize Illurninal p

!
-I

2 -08 -04 Potential, V vs A g / A g t

FIGURE 3. Current-voltage curves for 1 mH SO2 in 0.1 bl TBAP in CH3CN

at Pt, P-si p-InPzand P-usz. Irradiation wavelength: 632.8 nm(40 mW/cm 1. Taken from reference (27).
9

about 11% has been reported using 514.5 n r n (100 mWcn efficiency for the conversion of SO2 to S20:significant.

).

The solar to
be

i s expected

456
6.

PHOTOELECTROCHEMICAL REDUCTION OF

O2

The photoelectrochemical reduction of O2 t o H20z

i s an

indirect process.The early investigation into it was carried out by Calabrese and Wrighton (28). The photoelectrochemical process of reduction of 2-t-butyl-9,lO anthraquinone in CH3CN was carried out in the presence of CH3COOH using 632.8 nm radiation. A n ECE (electron transfer-chemicalelectron transfer) process occurs resulting in the formation of the corresponding hydroquinone. A 2% photoelectrochemical energy conversion
a s obtained for this process. The hydroquinone reacts with O2 efficiency w

to yield >0.18M H202 by the following scheme

Keita and Nadjo

(29) used

a single redox couple, sodium the regenerative photocells the following

9,lO-anthraquinone 2,6-disulphonate reaction occurs

2 HI
+

in

constructed with p-WSe2 and p-Si photocathodes where

O2

>

H202+

I2

(20)

The synthesis of H202 by the following route has also been proposed by the above authors Cata1yst
AQ > AQHZ

(21)
AQ

H2
AQH,
+

0 2 >

H 2 2

(22)

where AQ represents anthraquinone. This scheme i s similar to the one

457

proposed earlier; however, there is a possibility of a side reaction of H202 with AQH2 1. proposed (30 reducing the overall yield. The formation of H 0 at the 22 illuminated Ti02 film electrode by the sol-gel method has also been

7.

PHOTOELECTROCHEMICAL GENERATION OF H2
Perhaps one of the exciting interests in this field when

Fujishima and Honda reported (31) photoelectrolysis of H 0 a t n- Ti02 was 2 the generation of H2 at the cathode. As this electrolysis uses a wide bandgap semiconductor ( E =3.2eV), the practical utilisation of it has been g limited. The prospects of using small band gap semiconductors has been explored in the last few years by a large number of investigators (32-35). The previous attempts by others have already been reviewed (36-43)in the literature. The photoelectrochemical hydrogen evolution using metallised as the metal catalysts semiconductors have been investigated (44,55-60) increased the Gibbs free energy efficiency upto about 13%. Aspnes and Heller (44)proposed that the work function of the metal catalyst with reference to the semiconductor brings a true ohmic or nearly ohmic contact with a substantial collapse of the barrier between the metal and the semiconductor upon hydrogenation. Figure 4 depicts the work function of metals and band edges of semiconductors and the processes occurring at the s a finite delay time when semiconductor. It is observed (44) that there i no gas evolution takes place until the separate hydrogen and oxygen enveloped the catalyst islands are established. However, the oxide semiconductors produce trapping effects which are not reproducible. The

hydrogen evolution at small band gap semiconductors such as n-CdS would be accelerated by Rh or Ru than Pt. This conclusion is well supported by the hydrogen evolution on n-CdS deposited with Ru02 (44)and absence of it when deposited with Pt (for this discussion the work function of Ru02 is 4.8 eV s close to Ru metal). The formation of ohmic contact which i due to the surface damage during sputtering of metals onto the semiconductors has also been reported (46); this has been demonstrated for n-CdS where surface regions are sufficiently damaged. The hydrogen evolution at a Pt modified p-InP electrode has been investigated in detail (32). This modification produced an efficient and stable solar to chemical energy conversion efficiency of 9.2 % by etching the electrodes in Conc. HC1. The formation

458

A
Cds

z 3 a
I V
W J

-6

-1

-1;
?
-I3

-8

0 z
V W w I
I -

( a 1

ANODE

zn'+vz o

2 h++ n20

n-TiOp

CATHODE

2C-+ZH++#-HZ

FIGURE 4. A. Semiconductor band edges and work function of metals B. The band bendings of a semiconductor in assymnetric junctions
Taken from reference (441.

of minute Pt islands on InP i s recommended where the InP i s in direct contact with the solution. The deposition of Pd on the semiconductor i n the place of Pt produces a very poor response. The efficient cell performance
i s attributed to the interface states produced by hydrogen; the adsorption of hydrogen on the metal surface and consequently decreasing the metal

work function and the introduction of high barrier have been considered to be ineffective.

459

Several doped oxide materials have been considered for efficient production of hydrogen
Somarji's

in the photoelectrolysis experiments hydrogen from water

(34,351.

group

(35) produced

electrolysis by

illuminating Mg doped (p-type) and S i doped (n-type) iron oxides. The photoelectrochemical properties of p-CaFe204 and p-SrFe10022 with band gaps of 1.8 eV and 1.9 eV respectively have been considered for hydrogen generation (34). Figure 5 shows the band diagram for these semiconductors. The deposition of Pt on the surface of both electrodes increases the hydrogen evolution reaction. The conversion efficiency from light to H2 and O2 was estimated to be about The long term stability of CaFe204 is higher than Sr7Fe10022. Several other oxides having Fe in their lattice have been considered as photoanodes with band gap energies of about 2.1 eV on the basis of the stability considerations
(36-43). The kinetics of photoelectrochemical oxidation of water has been

considered at n-Ti02 semiconductor electrode (46-48). The possibility of

Current (log i)

FIGURE 5 . A description of the electron transfer process at CaFe 0 and band structure description for CaFe 0 and Sr2Fe100z24 e band formed by crystal field spligting 4 of iron g . s and d orbitals is shown. e 1,and a I hopping bands 8 1g with trigonal distribution of the lattice are also indicated in the figure. Taken from reference (34).

5.

460

photointercalation in semiconductors has been considered (49,501 and it has been shown that the intercalation in p-WSe2 causes a high overpotential for hydrogen evolution reaction. The quantity of hydrogen corresponding to
1 0

monolayers

coverage

has

been

obtained

by

heating

p-WSe

Tungsten-silicon and other modified electrodes have been examined for the stability in the continuous generation of H2 in photoelectrolysis (51). p-Si surface stabilised by hydrogen has been shown to produce H2 for more 2 t a c.d. 240 mA/cm with no degradation. The characteristics of than 48 h a

Ni modified p-Si have also been examined in KOH solutions (52). The metal catalysts incorporated into p-Si have been investigated for the hydrogen evolution (53) in acidic solutions. It has been shown that Pt/p-Si contact is nearly ohmic; good rectifying character develops by etching this electrode in alkali. A similar result has been obtained with a Au layer s increased a t covering p-Si. In effect this indicates the barrier height i
the junction. The structure of the metal layer plays a role in the photo
s coated with minute islands of the metal activity. If the semiconductor i

it causes H2 evolution at positive potentials than the bare Pt or bare

p-Si. A discontinuous metal covering produces a good photovoltaic activity
(53). Photosensitised reduction of water at Ru02 has also been examined (54) and

the

activation

energy

for

hydrogen

evolution

has

been

substantially changed by the addition of anthracene carboxylates. The photoevolution of H2 at metal catalysts has been examined by a number of investigators (55-60); conclusive evidence exists that the metal islands are necessary for a good activity. A short circuited photoelectrochemical cell has been used with sintered CdS pellets with P t deposits for the oxidation of HCOOH and simultaneous evolution of H2 (61);3 p o l of H2 in
180 minutes was generated with an input energy of

1.2 kJ m

-2 -1
s

The

simultaneous generation of H2 and 0 using Ti02 and R u ( b p y ) : +

2

has been

considered as a function of grain size and amount of Ti02 (62). The addition of thiourea and 2-aminopyridine has been shown to suppress the photocorrosion of Ti02 (65). materials for producing H

A physical model for water splitting to H2

has been described using semiconductors (63). The need for developing new
2

has also been emphasised (64,661. Popkirov and

Pleskov (67) proposed a new system for hydrogen production by water electrolysis and Siege1 and Schott (68) have suggested the optimisation of photovoltaic cells for hydr0gen.A derivatized p-InP has been used in the photoelectrochemical production of H2 (69).

The

generation

of

hydrogen

using

small

bandgap

semiconductors while stabilising from photo-corrosion has been quite challenging and has been innovatively solved by the concept of vectorial charge transfer in vertical and circular configurations (70,711.In this method a higher driving force for the decomposition of water has been obtained by the vectorial addition of voltages. The ultimate decomposition of water to hydrogen and oxygen occurs at the two Pt electrodes. A long term stability of the semiconductor i s reached by using a polysulphide or polyselenide medium (72). A polymer coated semiconductor electrode in place
of the naked electrode in the vectorial charge transfer assembly has also

been used

successfully

(73-75). The

production

of

H2

using

p-type

transition metal phosphides and p-type molybdinium sulphides have also been reported (76,77). The function of Co and Pt on p-InP in the evolution of H
2

has been explored by

Goodman and Wessels (78,791and Kobayashi et a1 has also been examined for water

(80). Pt

intercalated to K4Nb6017

decomposition (81).

8.

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