In-MOF-derived In₂S₃/Bi₂S₃ heterojunction for enhanced photocatalytic hydrogen production

Abstract

Transition metal sulfides are commonly studied as photocatalysts for water splitting in solar-to-fuel conversion. However, the effectiveness of these photocatalysts is limited by the recombination and restricted light absorption capacity of carriers. In this paper, a broad spectrum responsive In₂S₃/Bi₂S₃ heterojunction is constructed by in-situ integrating Bi₂S₃ with the In₂S₃, derived from an In-MOF precursor, via the high-temperature sulfidation and solvothermal methods. Benefiting from the synergistic effect of wide-spectrum response, effective charge separation and transfer, and strong heterogeneous interfacial contacts, the In₂S₃/Bi₂S₃ heterojunction demonstrates a rate of 0.71 mmol/(g∙h), which is 2.2 and 1.7 times as much as those of In₂S₃ (0.32 mmol/(g∙h) and Bi₂S₃ (0.41 mmol/(g∙h)), respectively. This paper provides a novel idea for rationally designing innovative heterojunction photocatalysts of transition metal sulfides for photocatalytic hydrogen production.

Graphical abstract

Keywords

photocatalytic hydrogen production / wide-spectrum response / metal sulfides / MOFs derivative / heterogeneous interfacial contact

1 Introduction

The photocatalytic water splitting technology has the potential to produce clean and renewable hydrogen energy with zero carbon emissions, providing a solution to the energy crisis and environmental pollution [1–8]. In numerous photocatalysts for water splitting, transition metal sulfides have attracted extensive attention due to their suitable energy band structures [9–17]. However, the most photogenerated carriers of single sulfides are prone to recombination, which limits their practical applications. To overcome this challenge, researchers have proposed the heterojunction construction as a crucial strategy to modify single sulfides and improve their photocatalytic hydrogen production [18–20]. Several sulfides heterojunction systems, such as MoS₂/g-C₃N₄ [21], Ag/Bi₂S₃/MoS₂ [22], and TiO₂/ZnIn₂S₄ [23], have been investigated. However, building a sulfide heterojunction system with excellent optical absorbance, effective charge separation and transfer, and tight interfacial contact remains a challenge.

Bi₂S₃ is a widely used transition metal sulfide semiconductor with a band gap of 1.3−1.7 eV, which possesses a unique wide-spectrum response capability. Miodyńska et al. [24] successfully constructed a TiO₂/Yb-Bi₂S₃ quantum dots (QDs) heterojunction by uniformly mixing Yb-doped Bi₂S₃ QDs with TiO₂ at high temperature, resulting in an enhanced photocatalytic hydrogen production activity. Huang et al. [25] developed a ternary Z-type heterojunction system of Bi₂S₃/TiO₂/MXene with a wide-spectrum response capacity, which also achieved an enhanced photocatalytic activity. However, the above Bi₂S₃ heterojunctions are designed purely by physical mixing, without achieving a tight contact between heterogeneous interfaces. Therefore, the design and construction of heterojunction systems require further investigation to achieve a strong interfacial contact, an efficient separation and transfer of photogenerated carriers.

In₂S₃ is also a versatile sulfide semiconductor with a tunable electrical structure and an excellent visible-light response ability. Hua et al. [26] obtained an enhanced photocatalytic hydrogen production performance by combining In₂S₃ and La₂Ti₂O₇ nanosheets, leveraging the opposite Zeta potentials at their contact interface. Sun et al. [27] synthesized a double S-type heterojunction system with a combination of In₂S₃, g-C₃N₄, and CoZnAl-LDH catalysts, achieving an improved photocatalytic hydrogen production activity. Further investigation is necessary to address the limitations of the In₂S₃-based heterojunction design, such as loose contact between catalyst interfaces, inadequate optical absorption, and sluggish charge separation ability. The morphology of the catalyst plays a crucial role in its charge transfer ability, and the derivatives of metal-organic frameworks (MOFs) have demonstrated a remarkable morphology controllability, including nanocages [28–31], polyhedra [32–35], nanospheres [36–39], and nanorods [40–43]. However, further designs are required to improve the charge transfer performance of the sulfide heterojunctions by leveraging the specific morphology of MOFs precursors. The strategy of in situ growth of MOFs-derived sulfide semiconductor on In₂S₃ can form strong heterogeneous interfacial contacts and an optimized energy band alignment, which will promote photogenerated carrier generation and transfer rate.

Herein, a novel method for creating an in situ In₂S₃/Bi₂S₃ heterojunction system is proposed using solvothermal and high-temperature sulfidation methods. This approach utilizes In-MOF as a precursor to form In₂S₃, which results in a short rod-like morphology that optimizes electron transfer pathways (Fig.1). By combining In₂S₃ with Bi₂S₃, a broad spectral absorption material is created that promotes strong heterogeneous interfacial contacts and an optimized energy band alignment. These features increase the generation and transfer rate of the photogenerated carrier, resulting in an enhanced performance. As a result, the In₂S₃/Bi₂S₃ heterojunction exhibits an optimized hydrogen production rate of 0.71 mmol/(g∙h), compared to In₂S₃ (0.32 mmol/(g∙h)) and Bi₂S₃ (0.41 mmol/(g∙h)). This innovative approach in morphology and heterostructure design provides a new strategy of developing efficient photocatalysts for hydrogen production.

2 Results and discussion

The synthetic process of the In₂S₃/Bi₂S₃ is depicted in Fig.1. Initially, the In-MOF precursor was prepared by a solvothermal method with indium nitrate (In(NO₃)₃·4H₂O) tetrahydrate as the indium source and terephthalic acid (C₈H₆O₄) as the organic ligand. Subsequently, the In-MOF was subjected to chemical vapor deposition using sulfur vapor, resulting in the production of black rod-like In₂S₃ in Ar gas. The synthesis of a well-defined In₂S₃/Bi₂S₃ heterojunction material was achieved by pyrolyzing the organic ligands of In-MOF at a high temperature [44]. Subsequently, the S²⁻ on the surface of the In₂S₃ attracted the Bi³⁺ in a high-temperature solvent, which promoted the in situ self-assembly of flower-like Bi₂S₃ on the surface of In₂S₃. In this process, polyvinyl pyrrolidone (PVP) was used to lower the nucleation barrier and promote the nucleation growth of Bi₂S₃. Finally, a well-defined In₂S₃/Bi₂S₃ heterojunction material was obtained. For comparison, In₂S₃ and Bi₂S₃ materials were also prepared. In summary, by using a simple and scalable pyrolysis method, a novel heterojunction material with a well-defined architecture was obtained.

The scanning electron microscope (SEM) and transmission electron microscope (TEM) measurements were performed to analyze the typical micromorphology and microstructure of the as-prepared samples (Fig.2). In₂S₃ is a short rod-shaped material with an average length and diameter of 5 and 2 μm, respectively (Fig.2(a)). The energy dispersive X-ray spectroscopy (EDX) elemental mapping images reveal a uniform distribution of In and S in In₂S₃ (Fig. S1). The In element in the In-MOF is derived from In ions, and the S element is obtained from high-temperature sulfur steam. During the high-temperature calcination, the organic chains in the hexagonal prism-shaped In-MOF undergo incomplete decomposition, resulting in a short rod contraction and ultimately leading to a twisted short rod morphology (Fig. S2). The flower-like morphology of the Bi₂S₃, with an average size of about 3 μm (Fig.2(b)), grows uniformly on the surface of the rod-like In₂S₃, forming a homogeneous In₂S₃/Bi₂S₃ heterojunction (Fig.2(c) and Fig.2(d)).

The structure of the composite was further confirmed by a high-resolution transmission electron microscope (HRTEM), which revealed lattice fringes of 0.285 and 0.315 nm, corresponding to the (222) plane of β-In₂S₃ and the (040) plane of Bi₂S₃, respectively (Fig.2(e)). This phenomenon indicates that In₂S₃ and Bi₂S₃ are in close contact to form a heterostructure. The EDX elemental mapping images of the hybrid material clearly reveal that the Bi element is primarily distributed on the outer surface of the material, while the In element is primarily distributed on the inside of the material, and the S element is evenly distributed throughout the material, demonstrating the formation of a heterogeneous structure (Fig.2(f)–2(i)). These results provide strong evidence that the Bi₂S₃, In₂S₃, and In₂S₃/Bi₂S₃ hybrid materials were synthesized successfully.

The structure of the as-prepared materials was further analyzed through X-ray diffraction (XRD) patterns and Raman spectra (Fig.3). The sharp XRD diffraction peaks demonstrate that the materials possess an excellent crystallinity (Fig.3(a)). In addition. the diffraction peaks of In₂S₃ and Bi₂S₃ correspond to the powder diffraction file (PDF) standard cards of β-In₂S₃ (JCPDS No. 65-0459) [45] and Bi₂S₃ (JCPDS No. 17-0320) [22], indicating that samples are successfully synthesized without impurity. The Raman peaks of Bi₂S₃ at 245, 421, and 965 cm⁻¹ correspond to the vibration modes of Bi-S [46], while In₂S₃ exhibits the A_1g Raman mode of β-In₂S₃ [47,48] (Fig.3(b)). Compared to the Raman peak at 965 cm⁻¹ of Bi-S in the Bi₂S₃, the vibration peak of Bi-S in the In₂S₃/Bi₂S₃ shows a blue-shift to 956 cm⁻¹, suggesting that the addition of Bi₂S₃ can generate a stress in the composite system [49,50], implying a strong interaction between the two materials.

To better understand the chemical bonding and surface electronic interactions of the materials, the high-resolution X-ray photoelectron spectroscopy spectra were analyzed. The XPS survey spectra reveal that the In₂S₃/Bi₂S₃ heterojunction contains three elements of In, Bi, and S, indicating that the composite is constructed (Fig.4(a)). The binding energies of In 3d in the composite (451.9 and 444.2 eV) are positively shifted compared to the In₂S₃ (451.2 and 443.7 eV), indicating a lower electron cloud density surrounding In³⁺ after the composite is formed (Fig.4(b)) [51]. The binding energies of Bi 4f in the composite (162.8 and 157.5 eV) are slightly lower than those in Bi₂S₃ (163.2 and 157.8 eV), illustrating an increase in electron cloud density around Bi^{3 +} after constructing the composite, which is contrary to In³⁺ (Fig.4(c)) [52]. Moreover, the high-resolution XPS spectra of S 2p for the three samples reveal the presence of S²⁻, as evidenced by two fitted peaks of S 2p_1/2 and S 2p_3/2 (Fig.4(d)). The S 2p fitting peaks of the hybrid materials shift to the negative direction compared to In₂S₃ and Bi₂S₃, demonstrating that the electron cloud density surrounding the S atom is redistributed after the heterojunction formation. The research findings indicate that the addition of Bi alters the coordination environment of S atoms and the electronic structure of the material surface, leading to the formation of In-S-Bi bonds on the surface of In₂S₃. These bonds facilitate the separation of electron-hole pairs by triggering surface electron redistribution [53,54]. It can be considered that heterojunction has a strong heterogeneous interface contact.

The photocatalytic hydrogen production activities of the In₂S₃, Bi₂S₃, and In₂S₃/Bi₂S₃ were investigated, utilizing sodium sulfite (Na₂SO₃) as the hole sacrificial agent. The In₂S₃/Bi₂S₃ heterojunction exhibits a maximum hydrogen production rate (0.71 mmol/(g∙h)) compared to In₂S₃ (0.32 mmol/(g∙h)) and Bi₂S₃ (0.41 mmol/(g∙h)) (Fig.5(a) and Fig.5(b)). Additionally, the In₂S₃/Bi₂S₃ heterojunction maintains a photocatalytic hydrogen production activity of 89.6% even after undergoing five catalytic cycles, proving its favorable stability (Fig.5(c) and Fig.5(d)). The SEM and TEM pattern show that the morphology of In₂S₃/Bi₂S₃ after 20 h photocatalytic test is well retained (Fig. S4). Moreover, the structure of In₂S₃/Bi₂S₃ after the photocatalytic reaction is almost unchanged (Fig. S5). Compared to other sulfide heterojunctions, In₂S₃/Bi₂S₃ exhibits a higher photocatalytic activity and can be considered as a promising photocatalyst for hydrogen production (Table S1).

To investigate the mechanism of the efficient photocatalytic performance of the In₂S₃/Bi₂S₃ heterojunction, the specific surface area, optical, and electrical properties of the photocatalysts were characterized. The Brunauer-Emmett-Teller (BET) surface area of the In₂S₃/Bi₂S₃ heterojunction is 30.0325 m²/g, which is much larger than that of the In₂S₃ (6.1001 m²/g) and Bi₂S₃ (16.3591 m²/g) (Fig. S6). The ultraviolet-visible (UV-Vis) spectra represent that In₂S₃ has a significant light absorption in the range of 300−450 nm, while In₂S₃/Bi₂S₃ displays a wide absorption band range from 300 to 800 nm, and the absorption peak red-shifts to 535 nm (Fig.6(a)). The wide-spectrum response of the In₂S₃/Bi₂S₃ can be attributed to the Bi₂S₃ with a narrow bandgap in the composite system [55].

The kinetics of the photogenerated charge carriers in the material was explored through electrochemical tests. The photocurrent density−time (I−t) curves show that the three samples exhibit an immediate response to intermittent light irradiation. Of the three samples, the In₂S₃/Bi₂S₃ heterojunction possesses the maximum photocurrent density, averaging around 2.34 mA/cm², demonstrating that heterojunction formation can effectively enhance the photogenerated carriers separation (Fig.6(b)) [47]. The photoinduced charge transfer ability of the materials was investigated using electrochemical impedance spectroscopy (EIS) (Fig.6(c)). The composite material shows the lowest Nyquist radius, demonstrating the reduced charge transfer resistance. This is due to the formation of a heterojunction, which facilitates charge transfer at the semiconductor/electrolyte interface [56]. Additionally, the recombination behavior of photogenerated carriers was analyzed by steady-state photoluminescence (PL) spectroscopy at a light illumination of 325 nm. All samples have an emission peak of around 470 nm. Interestingly, the composite material shows the lowest intensity, indicating that photoinduced charge recombination of the In₂S₃/Bi₂S₃ is alleviated, resulting in the maximum photocatalytic activity (Fig.6(d)) [57].

The Mott-Schottky (M-S) curves for In₂S₃ and Bi₂S₃ both exhibit positive slopes, which indicates that they are n-type semiconductors (Fig.7(a) and Fig.7(b)). The flat-band potentials (E_fb) of In₂S₃ and Bi₂S₃ are −0.30 and −0.04 eV, respectively (vs. the reversible hydrogen electrode (RHE)). The relationship between {\left(\alpha h\nu \right)}^2 and photon energy h\nu can be derived from the UV-Vis spectrum. From that, the band gaps (E_g) of In₂S₃ and Bi₂S₃ are calculated to be 1.66 and 1.45 eV, respectively (Fig.7(c) and Fig.7(d)). Ultraviolet photoelectron spectroscopy (UPS) was performed to determine the position of the work function, which reflected the ability of free electrons inside the material to escape from the Fermi level to the vacuum level. The secondary cutoff binding energies (E_cutoff) of In₂S₃ and Bi₂S₃ are calculated to be 17.02 and 16.80 eV, respectively (Fig.7(e)). According to the formula ɸ = h\nu−E_cutoff, the work functions of In₂S₃ and Bi₂S₃ are calculated to be 4.2 and 4.42 eV (vs. vacuum level E_vacuum), respectively. Combined with E_edge, the valence band maximum (VBM) of In₂S₃ and Bi₂S₃ are located at −5.76 and −5.8 eV (vs. E_vacuum), correspondingly. By considering the E_g of In₂S₃ and Bi₂S₃, the conduction band minimum (CBM) of In₂S₃ and Bi₂S₃ are calculated to be −4.0 and −4.35 eV (vs. E_vacuum), individually. These findings indicate that a type-II heterojunction is formed between In₂S₃ and Bi₂S₃ due to their proper energy band matching.

The energy level diagram and photocatalytic hydrogen production mechanism of In₂S₃/Bi₂S₃ are demonstrated in Fig.7(f), based on the calculation results. The complete photocatalytic process is explained as follows: The In₂S₃/Bi₂S₃ displays a strong light response capability, leading to an effective separation of photoinduced carriers under illumination. The type-II heterojunction of the composite system then generates a built-in electronic field, facilitating the transfer of photoinduced carriers and reducing carrier recombination. The electrons in the conduction band of In₂S₃ are transferred to Bi₂S₃, where they react with adsorbed protons from water to produce H₂. Simultaneously, the photoinduced holes in the valence band are transferred from the Bi₂S₃ to In₂S₃, where they congregate and undergo an oxidation reaction with the hole sacrificial agent (Na₂SO₃). As a result, an efficient photocatalytic hydrogen evolution process is completed. In addition, this carrier transfer route also avoids the oxidation of S²⁻ and improves the stability of the system.

3 Conclusions

In summary, a new photocatalyst was developed by combining Bi₂S₃ and In-MOF-derived In₂S₃, resulting in a In₂S₃/Bi₂S₃ heterojunction photocatalyst. The In₂S₃/Bi₂S₃ heterojunction has a maximum hydrogen evolution rate of 0.71 mmol/(g∙h) with a favorable stability. A series of photoelectrochemical tests demonstrate that the wide-spectrum response capability of Bi₂S₃, the fast electron transfer capability of the MOF-derived In₂S₃, and the heterogeneous interface of Bi₂S₃ and In₂S₃ in close contact synergistically improve the photocatalytic performance of the In₂S₃/Bi₂S₃. This paper provides an innovative approach to the construction of unique photocatalysts for hydrogen evolution in terms of morphology and heterojunction construction.

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