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3D/2D ZnIn2S4@La-Ti3C2 MXene boosting photocatalytic hydrogen production

Bing Yang , Yiqing Ran , Tingting Yu , Linlin Ge , Wenbin Chen , Jizhou Jiang

Composite Functional Materials ››

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Composite Functional Materials ›› DOI: 10.63823/20260402
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3D/2D ZnIn2S4@La-Ti3C2 MXene boosting photocatalytic hydrogen production
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Abstract

The high electron-hole recombination rate of photocatalysts remains a critical bottleneck that restricts the efficiency of photocatalytic H2 production. To mitigate this challenge, constructing dedicated electronic channels via rare earth metal doping has proven to be an effective strategy for enhancing the photoelectrochemical performance of photocatalytic systems. In this work, rare earth La-containing were anchored on the surface of two-dimensional (2D) Ti3C2 MXene through sodium borohydride reduction coupled with in-situ synthesis, and the as-prepared La-Ti3C2 MXene was subsequently embedded into three-dimensional (3D) ZnIn2S4 (ZIS) nanoflowers to fabricate a composite photocatalyst. Under optimized experimental conditions, the ZIS@La-Ti3C2 MXene composite demonstrates excellent photocatalytic H2 production activity, with a high rate of ~8406.67 μmol g-1 h-1. To elucidate the charge transfer mechanism, ultraviolet photoelectron spectroscopy (UPS) and in-situ irradiation X-ray photoelectron spectroscopy (ISI-XPS) were utilized to systematically investigate the carrier migration pathways within the composite. The results confirm efficient charge transfer at the interface between ZIS and La-Ti3C2 MXene, which remarkably suppresses electron-hole recombination. Femtosecond transient absorption spectroscopy (fs-TAS) jointly verify the ultrafast interfacial electron transfer pathway in ZnIn2S4@La-Ti3C2 MXene. The metallic La-Ti3C2 acts as an electron bridge to capture photoelectrons, prolonging carrier lifetime and suppressing charge recombination. This work develops a novel surface modification strategy and uncovers the synergistic effect of La doping in improving the separation efficiency of photogenerated carriers. By integrating rare earth elements with photocatalytic materials, this work offers a feasible approach to enhance photocatalytic H2 production efficiency, providing valuable insights for the design and development of high-performance photocatalytic systems.

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Photocatalytic H2 production / Ti3C2 MXene / ZnIn2S4 / In-situ synthesis

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Bing Yang, Yiqing Ran, Tingting Yu, Linlin Ge, Wenbin Chen, Jizhou Jiang. 3D/2D ZnIn2S4@La-Ti3C2 MXene boosting photocatalytic hydrogen production. Composite Functional Materials DOI:10.63823/20260402

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1. Introduction

Photocatalytic hydrogen production technology, which uses solar energy to drive photocatalysts to decompose water to produce hydrogen, is one of the ideal ways to solve the energy crisis and environmental pollution[1]. Since the discovery of the photodegradation of water over TiO2[2] by Fujishima and Honda in 1972, the field has experienced an evolution from wide-bandgap semiconductors to narrow-bandgap materials (carbon nitride, chalcogenides), and from a single catalyst to heterojunction/co-catalyst modifications. Photocatalytic H2 evolution offers a route for converting light into chemical energy. Its performance depends on light harvesting, charge separation and transport, surface reaction kinetics, and catalyst stability, rather than on charge recombination alone. In recent years, research has focused on two core issues: low photogenerated carrier separation efficiency and underutilization of the solar spectrum[3,4]. Overall, the field is in a period of transition from theoretical research to practical application, and breakthroughs are still needed in the in-situ characterization of surface reaction kinetics and charge transfer pathways[5,6].
The high recombination rate of photogenerated electron-hole pairs remains a critical bottleneck restricting the efficiency of photocatalytic hydrogen evolution[7,8], severely limiting the large-scale practical application of semiconductor photocatalysis in green hydrogen production[9]. To address this long-standing challenge, constructing directional electron transport channels via rare-earth metal doping has been proven an effective strategy to optimize photoelectrochemical performance and boost carrier separation efficiency[10,11]. Rare-earth-containing modifications are also established in photocatalysis. La-N sites on carbon nitride have been investigated for CO2 reduction, and lanthanide oxides have been combined with ZIS for H2 production. Ce-doped LaCoO3 for dye degradation provides another example of rare-earth-containing photocatalyst design[12,13]. Rare-earth metal doping confers multiple intrinsic advantages for photocatalytic systems. It optimizes the semiconductor band structure by inducing moderate lattice distortion and favorable defect sites, narrowing the band gap and extending the visible-light response range to improve solar energy utilization[14,15]. The unique 4f orbitals of rare-earth species serve as effective electron capture centers, accelerating charge separation, suppressing electron-hole recombination, and reducing interfacial charge transfer resistance to prolong carrier lifetime[16]. Although catalysts containing La have provided a precedent for CO2 reduction, the CO2 adsorption capacity, product selectivity, and air capture performance of this composite material have not yet been evaluated. Therefore, its potential applications in CO2 conversion still require dedicated research in the future. Additionally, rare-earth doping regulates semiconductor crystal growth and surface microstructure, increasing specific surface area and exposing abundant active sites while strengthening reactant adsorption. The strong electronic interaction between doped rare-earth atoms and substrate materials also enhances structural stability and catalytic durability, generating remarkable synergistic effects with 2D MXene substrates[17].
ZnIn2S4 (ZIS)[18,19] is a promising ternary layered chalcogenide photocatalyst for hydrogen evolution reaction (HER), featuring a suitable band gap (2.2~2.5 eV) and favorable visible-light response, as well as adequate thermodynamic driving force for proton reduction owing to its matched conduction band position[20-22]. Nevertheless, the practical HER activity of pristine ZIS is severely hampered by fast photogenerated electron-hole recombination, inferior electrical conductivity and limited structural stability, and conventional single modification strategies fail to fundamentally break through its performance bottleneck[17]. Common modification strategies include noble metal loading, heterostructure construction and defect engineering. For instance, loading Pt on ZnIn2S4 can enhance electron capture and provide active sites for the hydrogen evolution reaction. Another study demonstrated that constructing a TiO2/ZnIn2S4 heterojunction can facilitate rapid charge separation while retaining strong redox capabilities[23,24]. Introducing sulfur vacancies can regulate the electronic structure and promote carrier capture, but excessive defects may also accelerate the recombination of electron and hole pairs[18,25]. Although these strategies have the aforementioned advantages, a single strategy may not be able to simultaneously optimize charge separation, electron transport and surface reaction kinetics[26]. Therefore, combining ZIS with conductive MXene and La surface modification is helpful in exploring the complementary roles of different components in interface charge transfer and photocatalytic hydrogen evolution.
As a representative 2D transition metal carbide, Ti3C2 MXene possesses ultra-high conductivity, large specific surface area and superior hydrophilicity, which can synergistically optimize ZIS via constructing a Schottky heterojunction. Further incorporation of rare-earth La doping endows additional electron-trapping sites, maximizing the synergistic catalytic effect[27]. They are currently one of the most promising photocatalysts with large specific surface area, excellent Fermi energy levels and abundant active sites on the surface[28,29]. For the interaction sites of metals on Ti3C2Tx, anchoring is mainly achieved at the top, vacant, and bridge sites of Ti3C2Tx[30,31]. The anchoring of metals can effectively increase the interlayer spacing, provide more active sites, and increase the electron mobility. Ti3C2-based cocatalysts have been investigated with metal-sulfide photo-absorbers, and sulfur-vacancy engineering has been reported in ZIS/MXene composites [2,32]. Meanwhile, MXene regulates ZIS morphology to expose more active sites, strengthens reactant adsorption and enhances the composite’s cyclic stability[33].
In this work, we report the synthesis of a composite photocatalyst by modifying the traditional ZIS@Ti3C2 MXene system using rare-earth La as functional electron transport channels. Sodium borohydride was employed as the reducing agent to anchor La onto Ti3C2 MXene with varying loading contents. The morphological evolution and physicochemical properties of the resulting composites were systematically characterized. With increasing La content, the color of the composite samples gradually changed from greenish to blackish, which is presumably attributed to the variation in La concentration and its electronic effect. In-situ irradiation X-ray photoelectron spectroscopy (ISI-XPS) clearly revealed the modulation of electron cloud density in Ti3C2 MXene nanosheets and verified the directional migration of photogenerated electrons at the interface. Correspondingly, photocatalytic hydrogen evolution tests demonstrated that La modification substantially enhanced the hydrogen production efficiency of the composite. This structural modification effectively improved the separation and transport efficiency of photogenerated charge carriers. Given the favorable band structure and intrinsic hydrogen evolution activity of ZIS, constructing a ZIS@La-Ti3C2 MXene composite further regulated the electron transfer pathway, yielding remarkable synergistic enhancement. This work provides a new perspective for the application of rare-earth metal doping strategies in the field of solar-driven hydrogen production.

2. Experimental methods

2.1. Materials

High purity titanium aluminum carbide (Ti3AlC2, MAX) powder, zinc chloride (ZnCl2), indium chloride tetrahydrate (InCl3·4H2O), thioacetamide (TAA), anhydrous ethanol (C2H5OH), triethanolamine (C6H15NO3, TEOA), triethylamine (C6HN), triisopropanolamine (C9HNO3), acetonitrile (C2H3N) and chloroplatinic acid (H2PtCl6) were purchased from Aladdin Chemical Reagents. Lanthanum nitrate hexahydrate (La(NO3)3·6H2O), sodium borohydride (NaBH4), and hydrochloric acid (HCl) were purchased from Shanghai Macklin Biochemical Technology Co., Ltd. All chemicals were dissolved in deionized water. All chemicals used were of analytical grade.

2.2 Synthesis of ZIS and Ti3C2 MXene

A single ZIS catalyst was synthesized using a simple one-step solvent method. 0.5 mmol of ZnCl2, 1 mmol of indium chloride tetrahydrate and 2 mmol of TAA were dissolved in 30 mL of deionized water with continuous stirring and transferred to a PTFE-lined stainless-steel autoclave. The reaction temperature and time was set to 160 °C and 12 h, respectively, then the autoclave was cooled to room temperature and the product was removed. It was dried overnight in a vacuum oven at 40 °C and ground into yellow powders.
Ti3C2 MXene was obtained after conventional hydrochloric acid and LiF etching, 1.6 g of LiF was mixed with 20 mL of hydrochloric acid solution (HCl:H2O = 3:1) and then put into an oil bath and stirred for 30 min. 1 g of Ti3AlC2 was then added and the temperature was adjusted to 40 °C, and after stirring for 48 h, it was acid washed three times with 2 M HCl aqueous solution and then rinsed with deionized water several times until the supernatant blackened. The centrifuge was set at 5000 rpm, repeated three times for 1 min, and then filled with argon gas for protection, centrifuged for 10-15 min to collect the supernatant, and the precipitate was stored in the refrigerator.

2.3 Synthesis of ZIS@La-Ti3C2 MXene

After 0.1 g of Ti3C2 was weighed and ultrasonicated for 30 min, lanthanum nitrate hexahydrate (0.5, 1, 2, 4, and 8 mmol) was added dropwise to the solution while stirring. In the sample designation ZIS@La-Ti3C2 MXene (x), x denotes the amount of La(NO3)3·6H2O precursor added during synthesis, expressed in mmol, rather than the measured La content in the final composite. After stirring, the lanthanum was reduced by adding a NaBH4 solution of the corresponding concentration, and after 2 h the precipitate was washed several times by centrifugation. The precipitate was freeze-dried to obtain the La-Ti3C2 MXene. 50 mg of the above prepared La-Ti3C2 MXene was weighed and put into the precursor solution of ZIS for compounding, which was named ZIS@La-Ti3C2 MXene (x, x=0.5, 1, 2, 4, 8), according to the different molar La content. The steps are shown schematically in Fig. 1a.

2.4 Measurements and characterizations

The morphology and composition of the catalyst were characterized by scanning electron microscopy (SEM, SU8010 by Hitachi) and transmission electron microscopy (JEM-2010, TEM). The elemental composition of the catalyst was determined by energy-dispersive X-ray spectroscopy (EDS, FEI Talos F200X).) X-ray diffraction (XRD, Ultima IV by Rigaku) was operated at an acceleration voltage of 40 kV, a current of 40 mA, a scanning range of 5° to 80°. ISI-XPS was used to record the surface chemical states spectra of catalysts. Ultraviolet-visible spectrophotometry (UV-Vis DRS, Shimadzu UV-3600) was performed to characterize the energy band gap (Eg). The photocurrent (CHI660E, China) measured to evaluate photosensitivity of the catalyst. The Mott-Schottky curve (CHI660E, China) was tested in 200, 800, 1000 Hz. The catalyst was characterized by Fourier transform infrared spectroscopy (FTIR), and the Brunauer-Emmett-Teller (BET) method was used to test the structural properties of the powder using the Specific Surface & Pore Size Analyzer (3H-2000PMI). The femtosecond transient absorption spectroscopy (fs-TAS) data were collected on a transient absorption spectrometer using the MIRA 900 ultrafast laser system (Coherent, Inc., USA). By focusing the light through a sapphire crystal to generate the probe light, which was then pumped by the Pharos femtosecond laser to produce a 380 nm excitation pulse, transient absorption spectra were recorded at different time resolutions under an acetonitrile solvent in the range of 450 - 800 nm. Photoluminescence (PL) spectra were recorded using a Hitachi F-7000 fluorescence spectrometer under 350 nm excitation. Electron spin resonance (ESR) spectroscopy was performed using a Bruker A300 spectrometer. The sample was dispersed in methanol and subjected to ultrasonication. Subsequently, 50 mM DMPO (5,5-dimethyl-1-pyrroline N-oxide) solution was added to the mixture, followed by vigorous shaking.

2.5 Electrochemical test

The transient photocurrent response curves of the photocatalysts, electrochemical impedance spectroscopy (EIS) curves, and cyclic voltammetry (CV) curve were measured using an electrochemical analyzer (CHI660E, China) in a standard three-electrode system. A 0.1 mol·L-1 aqueous solution of potassium ferricyanide (K3[Fe(CN)6]) served as the electrolyte. A 300 W Xenon lamp was employed as the light source. The working electrode was prepared as follows: 2 mg of the photocatalyst was dispersed in 1 mL of deionized water, followed by ultrasonication for 10 min to ensure uniform dispersion. The resulting suspension was then drop-cast onto the surface of an indium tin oxide (ITO) substrate and allowed to dry naturally at room temperature.

2.6 Evaluation of Catalyst Hydrogen Production Performance

The photocatalytic hydrogen production experiments were carried out in a 100 mL hermetically sealed Pyrex glass reactor. This was done as follows: 15 mg of photocatalyst was homogeneously dispersed in 40 mL of aqueous solution containing TEOA as the sacrificial agent. A 300 W Xenon lamp equipped with a UV cut-off filter (λ ≥ 420 nm) was used as the light source. Hydrogen was collected at 0.5 h intervals and quantified using an on-line gas chromatograph (GC-9790II, Fuli). The stability and reusability of photocatalytic hydrogen production were tested by exchanging the gaseous products with argon and centrifuging and drying the catalyst after each cycle.

3. Results and discussion

3.1 Morphology and nanostructure testing

The morphology and structural features of the catalysts were derived from SEM images and TEM tests. The Ti3C2 MXene is a typical stepped laminar structure, whereas the La-Ti3C2 MXene surface after anchoring La-containing have sparse particles attached to the laminar surface, and the anchoring by the rare-earth metal can increase the layer spacing to some extent and provide active sites (Fig. 1b-e). In addition, as shown in Fig. S1, the larger-sized nanoflowers were broken into small pieces after being combined with layered Ti3C2 MXene, and obvious small-structured attachments were observed. The ZIS morphology is a standard nanoflower-like shape, and the observed lattice spacing of 0.32 nm corresponds to the (102)characteristic peak component of ZIS, while the 0.192 nm spacing is attributed to the (110) characteristic peak (Fig. 1f)[2]. To demonstrate the successful synthesis of ZIS@La-Ti3C2 MXene, XRD plots of the samples showed that the pristine ZIS displayed standard XRD diffraction peaks at 21.58°, 27.69°, 47.17°, 51.82°, and 52.11°, corresponding to PDF#72-0773 (Fig. 1g and Fig. S2)[29]. Its main characteristic peaks 21.58°, 27.69°, and 47.17° correspond to the (006), (102), and (110) lattices in the standard card, respectively[34]. It is noteworthy that, in addition to the diffraction peaks of the pristine ZIS, Al atoms sandwiched between the MAX layers during the etching process were successfully removed, and the typical Ti3C2 MXene morphology was formed. The specific manifestation is that the characteristic peak of Al at 39.00° is close to disappearing after etching, and the MXene phase is successfully obtained[35]. Meanwhile, the morphology of the La-Ti3C2 MXene lamellar structure is very different from that of the Ti3C2 MXene nanosheets, which may be due to the introduction of La. The peak intensity gradually increased with the increase of La content (0.5, 1, 2, 4, 8). The catalyst morphology is due to the in-situ growth of ZIS nanoflowers on the Ti3C2 MXene lamellar structure, which results in the composite catalyst peaks being closer to pure ZIS.
All the samples exhibit a broad absorption band at 3360~3500 cm-1, which can be attributed to the stretching vibration of the O-H bond in the adsorbed water molecules (Fig. S3). The absorption peak at 1406 cm-1 originates from the stretching vibration of external carbon-containing impurities or carbon oxidation products (such as C-O bonds)[36], and belongs to the common peak introduced during sample preparation. The Ti-C bond peak of MXene (620 cm-1) is clearly visible, and combined with the XRD results, it can be confirmed that the two are composites[37,38]. The Ti3C2 MXene characteristic peaks anchored by La-containing are essentially not observed.
The surface of the ZIS@La-Ti3C2 MXene photocatalysts was partially covered by anchored La-containing, resulting in more surface particles and a non-smooth surface (Fig. 1e). In addition, the doping of La plays a crucial role in separating the layered Ti3C2 MXene and suppressing the agglomeration of ZIS nanoflowers[39], which helps to increase the active sites of the ZIS@La-Ti3C2 MXene composites. EDS imaging provided further elemental analysis, revealing the uniform distribution of La, Zn, In, S, C, and Ti in the composite catalysts (shown in Fig. 1h). La was introduced through surface modification of Ti3C2 MXene, and the resulting material was denoted as La-Ti3C2 MXene. For ZIS@La-Ti3C2 MXene (4), EDS analysis gave a La content of 9.61 wt% and 2.78 at% (Table S1).
PL reflects the efficiency of charge separation and transfer on the catalyst surface. The PL emission intensity shows the rate of photo-induced recombination of electrons and holes, the stronger the intensity, the faster the recombination rate and the lower the photocatalytic efficiency. At the excitation wavelength of 325 nm, the emission bands are distributed in the range of 375~600 nm. As shown in Fig. 2a, with the increase of La-doped Ti3C2 MXene, the emission intensity of PL gradually decreases compared with that of single ZIS and ZIS@Ti3C2 MXene. Obviously, the data in the figure indicate that the doped sample has the lowest emission intensity and a higher separation efficiency of photogenerated carriers. Therefore, the photogenerated carrier recombination rate of ZIS@La-Ti3C2 MXene is reduced, and its photocatalytic activity is the highest. The photoluminescence intensity of ZIS@La-Ti3C2 MXene is significantly lower than that of ZIS, indicating that the recombination of photogenerated carriers is further suppressed[38]. La-Ti3C2 MXene is intercalated within the flower-like ZIS, reducing the recombination rate of e-/h+ and enhancing the photocatalytic rate. To further investigate the interface-induced photo-induced charge transfer between MXene and ZnIn2S4, in-situ irradiation X-ray photoelectron spectroscopy (ISI-XPS) was performed on the samples. The elemental peaks observed in the full spectrum (Fig. 2d) are consistent with the mapping results[39]. As shown in Fig. 2f, without light irradiation, ZIS@La-Ti3C2 MXene exhibits four peaks at 855.06, 838.36, 830.86 and 827.41 eV, respectively, resulting from the splitting of the La 3d3/2 and La 3d5/2 orbitals. The binding energy of La 3d undergoes a negative shift after light irradiation, indicating an increase in electron density in La-MXene under light irradiation[40]. Similarly, as shown in Fig. 2e, the characteristic peak at 284.9 eV is attributed to the C-C bond. After light irradiation, this characteristic peak undergoes a negative shift, with a binding energy change of 0.09 eV. The in-situ generation of ZIS on La-Ti3C2 MXene causes a change in the binding energy of the C-C bond at the interface. The change in electron density provides direct evidence for charge transport at the ZIS@La-Ti3C2 MXene interface under the same light irradiation conditions. Under light irradiation, the La 3d peak of ZIS@La-Ti3C2 MXene shows a significant negative shift of approximately 0.81 eV, while the Zn 2p, In 3d, and S 2p peaks remain basically unchanged. This contrast indicates that the excited electrons are efficiently extracted from ZIS and accumulate on the La-Ti3C2 MXene side, directly proving the existence of interface directional electron transfer. During the photoreaction hydrogen production process, photo-generated electrons migrate from ZIS to La-Ti3C2 MXene, accelerating mass transfer, which is consistent with the spectral heat map in Fig. 2b-c, providing direct evidence for electron migration[41].
The fs-TAS with a probe at 635 nm was employed to investigate the photocarrier relaxation dynamics of bare ZnIn2S4, La- La-Ti3C2 MXene, and the ZIS@La-Ti3C2 MXene (4) heterojunction. Both distinct ground-state bleach (GSB, negative ΔA) and excited-state absorption (ESA, positive ΔA) signals are observed in the 2D pseudo-color plots and time-resolved transient spectra of all samples. Bare ZnIn2S4 exhibits weak GSB signals with rapid attenuation, attributable to severe intrinsic electron-hole recombination resulting from the lack of efficient trapping sites. La-Ti3C2 MXene shows negligible GSB but prominent ESA responses, a feature that arises from its metallic characteristic and outstanding electron storage capacity. In contrast, the ZIS@La-Ti3C2 MXene composite exhibits drastically strengthened GSB and ESA signals simultaneously, confirming both the intimate contact between the two components and the efficient generation of photocarriers at the heterointerface. This observation is consistent with the carrier regulation behavior reported for other ZIS/MXene composite photocatalysts.
The normalized decay traces probed at 635 nm were fitted using a tri-exponential function, in which τ1 is assigned to ultrafast intralattice electron diffusion, τ2 to electron trapping at defects or the heterointerface, and τ3 to radiative electron-hole recombination. For pristine ZIS, τ1 = 0.83 ps, τ2 = 2.87 ps, and τ3 = 13.9 ps, indicating that most photoelectrons recombine rapidly rather than participating in surface redox reactions. Bare La-Ti3C2 MXene shows τ1 = 0.98 ps, an extremely long trapping lifetime τ2 = 19.38 ps, and a moderate recombination lifetime τ3 = 49.1 ps. However, the absence of significant GSB signals confirms that negligible photoinduced carriers are generated under visible-light excitation. For the ZIS@La-Ti3C2 MXene (4) composite, τ1 = 0.89 ps, which falls between the values of the two single components, suggesting that photoelectrons generated in ZnIn2S4 diffuse quickly toward the heterointerface upon illumination. The unique interfacial trapping component with τ2 = 10.08 ps serves as direct spectroscopic evidence for the role of metallic La-Ti3C2 MXene as an ultrafast electron transfer highway, which extracts photoelectrons from ZIS and traps them on the MXene surface. Notably, the composite exhibits the longest recombination lifetime τ3 = 61.29 ps among all three samples, demonstrating that the built-in internal electric field at the S-scheme heterointerface effectively promotes spatial charge separation and thus dramatically suppresses charge recombination[42].
Collectively, the fs-TAS results reveal accelerated interfacial charge transfer and prolonged carrier lifetimes in the ZIS@La-Ti3C2 MXene composite, providing insight into the charge-carrier dynamics of the proposed type-I heterojunction. Upon photoexcitation of ZIS, the conductive La-Ti3C2 MXene facilitates the extraction and transport of photogenerated electrons at the interface. These processes contribute to the formation of a longer-lived carrier population, potentially increasing the availability of electrons for photocatalytic hydrogen evolution. The observed carrier dynamics thus provide a kinetic basis for understanding the enhanced hydrogen evolution activity of the composite[43].

3.2 Catalyst Composition and Photogenerated Carrier Dynamics

The light absorption properties of the catalysts are one of the important indicators to evaluate the performance. The UV-visible absorption spectra of the prepared samples Ti3C2 MXene, ZIS, ZIS@La-Ti3C2 MXene, and ZIS@La-Ti3C2 MXene (x) are shown in Fig. 4a. It is clear that the catalyst exhibits strong absorption in the range of 420~1000 nm. It can be seen that the ZIS@La-Ti3C2 MXene (x) composite photocatalyst exhibits considerable enhancement in visible light absorption. The results indicate that the doping of La-containing on the surface of Ti3C2 nanosheets is beneficial for enhancing the visible light absorption. The Eg of ZIS can be calculated using the following equation[35,44,45]:
${\left(\mathit{\alpha }\mathit{h}\mathit{v}\right)}^{1/\mathit{n}}\mathit{ }=\mathit{ }\mathrm{A}(\mathit{h}\mathit{v}\mathit{ }-{\mathit{E}}_{\mathit{g}}\mathit{ })$
where α is the absorption coefficient, h is Planck’s constant, hv is the photon energy, v is the incident photon frequency, A is the proportionality constant and Eg is the band gap energy of the sample (n = 1/2 for direct-gap semiconductor photocatalysts and n = 2 for indirect-gap semiconductor photocatalysts). As shown in Fig. 4b, the derived bandgap of ZIS is approximately 2.4 eV, consistent with previously reported values in the literature.
Mott-Schottky measurements were performed to investigate the band alignment and carrier transport behaviors of pristine ZIS and La-Ti3C2 MXene heterostructure, with saturated Ag/AgCl electrode serving as the reference electrode (Fig. 4c-d). All potential values were converted to the reversible hydrogen electrode (RHE) scale at 25 °C via the equation ERHE = EAg/AgCl + 0.197 + 0.0592 × pH. A conversion offset of 0.61 V was adopted for the neutral electrolyte used in this work. The flat band potentials (Efb) were extracted from the x-intercept of linear tangents of Mott-Schottky plots, which were -0.68 V and -0.60 V vs Ag/AgCl for bare ZIS and La-Ti3C2 MXene, respectively. For n-type semiconductors, the conduction band edge ECB is 0.2 V more negative than flat band potential[46], following the relation ECB = Efb(RHE) - 0.2 V. The estimated conduction-band potentials are -0.19 V for La-Ti3C2 MXene and -0.27 V for ZIS versus RHE. Combining these estimates with the optical gaps labeled in Fig. 4b using EVB = ECB + Eg gives VB potentials of +0.49 and +2.13 V versus RHE, respectively. Both conduction band positions are more negative than the thermodynamic redox potential of H+/H2 (0 V vs RHE), confirming sufficient reduction capability for photocatalytic hydrogen evolution[47]. The quantitative relationship between the fitted slope and donor carrier concentration is derived from the standard Mott-Schottky equation, with full parameter definitions, constant values and calculation formulas provided in Section S1. An increase in the slope indicates a decrease in the carrier concentration within the ZIS. Linear fitting of the linear segment of Mott-Schottky plots delivers slopes of 1.54 and 2.54 for pristine ZIS and ZIS@La-Ti3C2 MXene composite, respectively. The higher slope of the composite sample indicates a lower carrier concentration in its sulfide matrix[48]. After forming Schottky heterojunction between ZIS and the metallic La-Ti3C2 MXene, the potential difference exists between the Fermi levels at the interface. Free electrons in the conduction band of ZIS continuously migrate toward the conductive La-Ti3C2 MXene substrate and accumulate at the heterojunction interface, resulting in the formation of an electron-depleted layer in the sulfide bulk. Although the bulk carrier density of ZIS decreases after recombination, the photo-generated electrons that migrate to the La-Ti3C2 MXene surface are spatially isolated from the valence-band holes, which greatly suppresses electron-hole separation and recombination[49]. This is consistent with the significantly prolonged carrier lifetime observed in femtosecond transient absorption spectroscopy. The directional charge transport driven by the built-in electric field at the interface substantially enhances the utilization efficiency of effective reducing electrons, ultimately optimizing the photocatalytic hydrogen evolution kinetics.
The separation and transport of photogenerated charge carriers are important factors governing photocatalytic hydrogen evolution. As shown in Fig. S4a, ZIS@La-Ti3C2 MXene exhibited a substantially higher transient photocurrent density (~15.6 μA·cm-2) than pristine ZIS (~3.2 μA·cm-2), corresponding to an approximately 4.9-fold enhancement. This enhanced photo response suggests more efficient charge separation and collection upon the incorporation of La-Ti3C2 MXene, consistent with its role in facilitating interfacial electron transfer and transport. These results support improved charge-carrier utilization in the composite, which contributes to its enhanced photocatalytic hydrogen evolution activity. Since ECSA could not be reliably determined from single-scan-rate CV measurements, the peak current span (ΔI = Imax - Imin) at 100 mV/s, normalized to the geometric electrode area (1 cm2), is used here as a qualitative indicator of the electrochemically accessible surface (Table S2). All samples were measured under identical conditions (-0.5 to 1.0 V vs. Ag/AgCl, 100 mV/s, 1 cm2). The ΔI values follow the order: ZIS (4.0640 mA/cm2) > ZIS@Ti3C2 MXene (2.9470 mA/cm2) > Ti3C2 MXene (2.6220 mA/cm2) > ZIS@La-Ti3C2 MXene (4) (1.9173 mA/cm2) > La-Ti3C2 MXene (0.8970 mA/cm2). However, given that ZIS@La-Ti3C2 MXene (4) exhibits the highest photocatalytic hydrogen production activity, the above CV results indicate that the performance improvement is not simply due to the simple increase in accessible surface area, but rather results from the improvement of interface charge transfer and the electron bridge effect of La-Ti3C2 MXene, which has been confirmed by the fs-TAS results. The CV curves and EIS curves in Fig. S4b and Fig. 4e clarify the redox capacity as well as the electron transfer ability of the catalysts. There are obvious redox peaks in the CV plots, indicating that the catalysts possess the ability to oxidize H2O to generate ROS. The radius of the arc in the EIS indicates the electron transfer resistance in the catalyst, and it is obvious that the ZIS@La-Ti3C2 MXene has a stronger electron transfer ability after compounding. To further study the charge separation and transfer behavior of ZIS and ZIS@La-Ti3C2 MXene and investigate the mechanism of enhanced photocatalytic hydrogen evolution performance, UPS testing was conducted. In order to determine the work function (Φ) values of ZIS and ZIS@La-Ti3C2 MXene, ultraviolet photoelectron spectroscopy tests were conducted on both single and composite catalysts. As shown in Fig. 4f-g, the work functions of ZIS and ZIS@La-Ti3C2 MXene were measured to be 4.82 and 4.78 eV respectively.
Obviously, ZIS has a larger work function compared to the composite materials, indicating that it has a slightly deeper Fermi level[50]. This results in the flow of electrons during the electron transfer process being from ZIS to ZIS@La-Ti3C2 MXene. This result is consistent with the change in electron cloud density observed in the ISI-XPS illumination and blank control mentioned above. Next, ESR measurement was used to verify the existence of active species during the photocatalytic hydrogen production process. Using DMPO as a scavenger, the test was conducted 10 min after visible light irradiation. From Fig. 4h-i, it can be seen that under dark conditions, there was no signal fluctuation on the photocatalyst, indicating that no electrons or holes were generated in the system. After 10 min of irradiation, the characteristic peak signals with relative intensities of 1:1:1:1 and 1:2:2:1 were observed, which are attributed to DMPO-·O2- and DMPO-·OH, respectively [51,52].
The contact angle test proved that the surface hydrophilicity of the catalyst decreased after anchored by rare earth metal La, while the pure ZIS itself has a small contact angle of 35.5°, which is favorable for the aqueous phase reaction (Fig. S5)[39]. The contact angle of pure Ti3C2 MXene is 37.0°, which also belongs to hydrophilic materials. After composite, ZIS@La-Ti3C2 MXene maintains relatively good wettability, which facilitates the adsorption of polar molecules of sacrificial agent TEOA to participate in the next hydrogen precipitation reaction.

3.3 Photocatalytic hydrogen production performance experiment

The nitrogen adsorption and desorption tests indicated that the specific surface area and total pore volume of the different catalyst samples were mainly determined by the presence of ZIS. ZIS has a flower-like structure with abundant active sites and a large specific surface area, while the layered material Ti3C2 MXene has a relatively smaller specific surface area[30]. For the composite, the average pore diameter was between 11.60 and 22.08 nm (Fig. S6 and Table S3). Although the difference in specific surface area and pore diameter was not significant, they still had a slight impact on the hydrogen production capacity.
The photocatalytic hydrogen production performance of the ZIS@La-Ti3C2 MXene catalyst was evaluated as shown in Fig. 5. In the work, pristine ZIS and ZIS@La-Ti3C2 MXene (x) samples doped with different proportions of La were tested for yield. The results showed that the catalyst achieved the highest hydrogen production efficiency (1702.97 μmol·g-1·h-1) when the La doping ratio was 4 mmol (Fig. 5a, Fig. S7). The hydrogen production efficiency of the catalyst ZIS@Ti3C2 MXene was not very high, and it is even slightly lower than that of ZIS. The layered Ti3C2 MXene is interwoven between the flower-like ZIS structures, causing the flowers to break apart, and the active sites to decrease, thereby resulting in a decline in performance. Subsequently, we focused on whether the doped ZIS@La-Ti3C2 MXene catalysts had specific hydrogen production efficiencies in the face of different sacrificial agents to further evaluate the hydrogen precipitation performance. The results showed that the sacrificial agent TEOA would provide higher hydrogen production performance (Fig. 5b). Similarly, after multiple tests and condition screenings (Fig. S8), it was determined that with a catalyst dosage of 15 mg and a TEOA volume of 4 mL, a higher hydrogen production efficiency could be achieved. The composite ZIS@La-Ti3C2 MXene (4) catalyst with the addition of TEOA sacrificial agent along with 8% H2PtCl6 in Fig. 5c exhibited an excellent photocatalytic hydrogen precipitation rate of 8406.67 μmol·g-1·h-1, which was 45.19 times higher than that of the pristine ZIS without sacrificial agent. The obtained performance was 5.96 times higher than that of the addition of TEOA sacrificial agent only. Further tests were conducted to evaluate the reusability of this catalyst. Five cycles of experiments were carried out. During the repeated hydrogen production experiments (Fig. 5d), a slight decrease in the hydrogen production rate could still be observed. Overall, there were no significant changes. After multiple cycles, the catalyst still maintained a high intensity of XRD characteristic peaks (Fig. S2), indicating that it continuously utilized the surface-active sites for catalysis during hydrogen production and was stable without significant changes, demonstrating excellent stability.

3.5 Analysis of the photocatalytic mechanism

Based on the above experimental results, we propose the mechanism for enhancing the activity of photocatalyst ZIS@La-Ti3C2 MXene (Fig. 6). Based on the band position and spectroscopic and electrochemical observations, an I-type heterojunction model was proposed for ZIS@La-Ti3C2 MXene. The CB and VB potentials of ZIS were estimated to be -0.27 V and +2.13 V (relative to RHE), respectively, corresponding to an energy band gap of 2.40 eV. The corresponding values for La-Ti3C2 MXene were -0.19 V and +0.49 V (relative to RHE), with an optical band gap of 0.68 eV. Under this band description, both energy band edges of La-Ti3C2 MXene were within the band gap of ZIS, exhibiting typical I-type heterojunction band alignment characteristics. Electrons can rapidly transfer from ZIS to the La-Ti3C2 MXene surface, as Ti3C2 MXene at the La-containing termination exhibits electrical conductivity. Moreover, contact angle data indicate that ZIS@La-Ti3C2 MXene (4) is more prone to surface water adsorption. Under visible light irradiation, ZIS generates electron-hole pairs by exciting from the valence band to the conduction band. The photogenerated electrons can then transfer from the conduction band of ZIS to the low-energy conduction band state of La-Ti3C2 MXene and migrate to accessible surface reduction sites. The estimated electron acceptor energy level was -0.19 V (relative to RHE), still more negative than the H+/H2 equilibrium potential, indicating that the hydrogen evolution reaction is thermodynamically feasible. The MXene-containing medium promotes electron transport, while the La-containing surface modification affects the local interface environment and the utilization efficiency of transferred electrons. Under the sacrificial agent-assisted reaction conditions, the process of TEOA consuming holes on the accessible ZIS surface can compete with interface hole transfer and recombination[17,37]. Therefore, efficient electron transport, surface hydrogen evolution, and hole clearance caused by TEOA collectively provide evidence for the enhanced activity in the proposed I-type framework[53]. The PL emission weakening, impedance response changes, and longer transient components observed by fs-TAS are consistent with the changes in carrier relaxation and interface transport. Compared to the ZIS@La-Ti3C2 MXene control group without lanthanum, the higher activity further supports the positive effect of lanthanum modification[54]. Throughout the entire experimental process, TEOA also consumes the photogenerated holes on the VB and produces oxidation products.

4. Conclusions

In summary, a La-modified ZnIn2S4@Ti3C2 MXene composite was successfully prepared by sequential MXene surface modification and integration with ZIS nanoflowers. Under identical reaction conditions without H2PtCl6, ZIS@La-Ti3C2 MXene (4) exhibited an H2 evolution rate of 1702.97 μmol g-1·h-1, exceeding those of pristine ZIS and the La-free ZIS/MXene composite. This comparison demonstrates an additional activity enhancement associated with La modification. Further optimization using TEOA and H2PtCl6 increased the H2 evolution rate to approximately 8406.67 μmol g-1·h-1. To elucidate the intrinsic interfacial charge transfer mechanism and carrier dynamic behavior, fs-TA and ISI-XPS were utilized to systematically probe the carrier migration pathways and transport kinetics inside the composite material. The results demonstrate that efficient and fast charge transfer occurs at the compact heterointerface between ZIS and La-Ti3C2 MXene, which markedly suppresses the radiative recombination of photogenerated carriers and prolongs the lifetime of excited electrons. Additionally, the distinct synergistic effect between La doping and 2D MXene further enhances the separation, migration and utilization efficiency of photogenerated charge carriers. This work develops a novel surface modification strategy for rare-earth functionalized MXene-based photocatalysts, and deeply reveals the synergistic role of La doping in elevating the separation efficiency of photogenerated carriers. By integrating rare-earth elements with photocatalytic materials, this study provides a feasible route to enhance the efficiency of photocatalytic hydrogen evolution, offering valuable guidance for the design and development of high-performance photocatalytic systems.
Declaration of Competing Interest
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this article. Jizhou Jiang is Editor in Chief, and Tingting Yu is an Editorial Board Member of this journal and they were not involved in the editorial review or the decision to publish this work.
Acknowledgments
This work was supported by the National Natural Science Foundation of China (No. 22506066), the Key Research and Development Project of Lianyungang City (Social Development) (No. SF2516), the Key Project of Scientific Research Plan of Hubei Provincial Department of Education (No. D20241501), the Lianyungang City's Challenge and Response (Technology Transfer) project (No. CA202201), the Science and Technology Innovation Project of Jiangsu Province (No. BY20240933), the Natural Science Foundation of Jiangsu Province (No. BK20181074), the China Postdoctoral Science Foundation (No. 2021M691327), the Jiangsu Postdoctoral Science Foundation (No. 2021K313C), the Postgraduate Research & Practice Innovation Program of Jiangsu Province (No. SJCX25_2113), the Postgraduate Research & Practice Innovation Program of Jiangsu Ocean University (No. KYCX2024-37).
Authors Contributions
Conceptualization, Tingting Yu; Methodology, Tingting Yu; Software, Bing Yang; Validation, Yiqing Ran and Linlin Ge; Formal Analysis, Bing Yang; Investigation, Yiqing Ran; Resources, Tingting Yu; Data Curation, Bing Yang; Writing-Original Draft Preparation, Bing Yang; Writing-Review & Editing, Tingting Yu and Jizhou Jiang; Visualization, Bing Yang and Yiqing Ran; Supervision, Wenbin Chen and Jizhou Jiang; Project Administration, Tingting Yu; Funding Acquisition, Tingting Yu and Jizhou Jiang.

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