Supporting Information

for

Experimental and DFT Insights on Microflower g-C3N4/BiVO4

Mohamad Fakhrul Ridhwan Samsudina, Habib Ullahb, Robabeh Bashiric, Norani Muti
Mohamedc, Suriati Sufiana, c*, Yun Hau Ngd

a Chemical Engineering Department, Universiti Teknologi PETRONAS, 32610, Bandar Seri

b Renewable Energy Group, College of Engineering, Mathematics and Physical Sciences,

c Centre of Innovative Nanostructures & Nanodevices (COINN), Universiti Teknologi

d School of Energy and Environment, City University of Hong Kong, Kowloon, Hong Kong
SAR, P. R. China.

Corresponding authors: S. Sufian ([email protected]) / Tel: +605-3687587

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 Figure S1: Optimized crystal structures of (a) gC3N4, (b) BiVO4 and (c) g-C3N4/BiVO4.

The interaction energy (adsorption) was calculated with the help of eq 1.

∆Ead = Eg - C3N4/BiVO4 ― (Eg - C3N4 + EBiVO4) (1)

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In this case equation, Eg‑C3N4/BiVO4, Eg‑C3N4, and EBiVO4 represent the total energy of the relaxed

g-C3N4/BiVO4 system, monolayer g-C3N4, and BiVO4 slab, respectively. Meanwhile, the band

alignment of all these three species was calculated from the difference of Evac and Fermi energy

level (EF), using this relation Φ = Evac – EF.

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Figure S2: Band structures of (a) BiVO4, (b) g-C3N4, and (c) g-C3N4/BiVO4 heterojunction;

here the Fermi energy level is set to zero [1].

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Figure S3. Partial density of states plots of (a) BiVO4, (b) g-C3N4, and (c) g-C3N4/BiVO4

heterojunction. The vertical dashed lines represent the work function and the energy is in eV

versus vacuum.

The contribution of individual atoms which constitute the VBM and CBM; the partial density

of state (PDOS) are calculated, as shown in Fig S3a-c. The VBM and CBM of g-C3N4, BiVO4,

and heterojunction were simulated from the density of state (DOS) simulations. In Fig S3a, the

VBM of BiVO4 is from the bonding orbitals O 2p, situated at -7.03 eV (vs vacuum) while that

of CBM (-4.57 eV vs vacuum) is made of anti-bonding orbitals of V 5d. So, the VB is mainly

composed of O orbitals while its bottom section is from the equal contribution of V and Bi

orbitals. Moreover, the CB of BiVO4 is mainly composed of the anti-bonding orbitals of V

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atoms and the lower density section is made of the hybridized orbitals of O and Bi atoms. The

VB and CB of g-C3N4 are equally occupied by orbitals of N and C. Here, the VBM and CBM

are situated at -5.74 and -3.07 eV (vs vacuum), respectively.

Figure S4: Electrostatic potential maps of (a) g-C3N4, (b) BiVO4, and (c) g-C3N4/BiVO4

heterojunction. The red dashed lines represent Fermi energy level, blue denotes vacuum energy

level and the green dashed circle highlights the interface of g-C3N4/BiVO4 heterojunction.

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Figure S5: Averaged electron density difference (Δρ) along the Z-direction for g-C3N4/BiVO4.

The green and yellow shaded areas indicate electron accumulation and donation, respectively.

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 Figure S6: Photoelectrocatalytic hydrogen production of 0.8 wt.% g-C3N4/BiVO4 using
different water source.

Table S1: VBM, CBM (at vacuum level), and Band Gap (in unit of eV) of BiVO4, g-C3N4, and

g-C3N4/BiVO4.

Species VBM CBM Bandgap Work

Apparent Quantum Efficiency (AQE) of the as-developed Photocatalyst

The AQE was measured under the same photoelectrocatalytic hydrogen evolution conditions

at 420 nm. The AQE is calculated using the following equation:

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 2 𝑥 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 ℎ𝑦𝑑𝑟𝑜𝑔𝑒𝑛 𝑒𝑣𝑜𝑙𝑢𝑡𝑖𝑜𝑛
𝐴𝑄𝐸 = 𝑥 100%
𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑖𝑛𝑐𝑖𝑑𝑒𝑛𝑡 𝑝ℎ𝑜𝑡𝑜𝑛𝑠

The details of the AQE definitions and measurements has been comprehensively discuss

elsewhere [2,3].

Table S2: Summary of the photoelectrocatalytic hydrogen production and apparent quantum

efficiency (AQE) of the as-developed photocatalysts.

Hydrogen Production
Sample AQE (%) at 420 nm
(mmol/h)

BiVO4 9.5 1.90

g-C3N4 11.9 2.37

0.1 wt.% g-C3N4/BiVO4 13.5 2.69

0.4 wt.% g-C3N4/BiVO4 18.3 3.63

0.8 wt.% g-C3N4/BiVO4 21.4 4.27

1.2 wt.% g-C3N4/BiVO4 15.9 3.12

Reference
[1] Safaei, J., et al., Enhanced photoelectrochemical performance of Z-scheme g-C3N4/BiVO4

photocatalyst. Applied Catalysis B: Environmental, 2018. 234: p. 296-310. DOI:

10.1016/j.apcatb.2018.04.056

[2] Cui, E., et al. In-situ hydrothermal fabrication of Sr2FeTaO6/NaTaO3 heterojunction

photocatalyst aimed at the effective promotion of electron-hole separation and visible light

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absorption. Applied Catalysis B: Environmental, 2019. 241: 52 – 65. DOI:

10.1016/j.apcatb.2018.09.006

[3] Raziq, F., et al. Enhanced cocatalyst-free visible-light activities for photocatalytic fuel

production of g-C3N4 by trapping holes and transferring electrons. Journal of Physical

Chemistry C, 2016. 120: 98 – 107. DOI: 10.1021/acs.jpcc.5b10313

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