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Article

Ti3AlC2 MAX/MXene for Hydrogen Generation via Photocatalytic Hydride Hydrolysis

by
Hani Nasser Abdelhamid
Department of Chemistry, College of Science, Imam Mohammad Ibn Saud Islamic University (IMSIU), Riyadh 11623, Saudi Arabia
Inorganics 2025, 13(2), 44; https://doi.org/10.3390/inorganics13020044
Submission received: 12 January 2025 / Revised: 31 January 2025 / Accepted: 3 February 2025 / Published: 5 February 2025
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Abstract

:
Reducing dehydrogenation temperature while preserving high hydrogen generation capacity obstructs the hydrolysis of sodium borohydrides (NaBH4). The two-dimensional (2D) MAX phase of titanium aluminum carbide (Ti3AlC2) and MXene (Ti3C2Tx) multilayers was investigated for hydrogen generation via NaBH4 hydrolysis with and without light. The material was characterized using X-ray diffraction (XRD), Fourier transform infrared (FT-IR), transmission electron microscopy (TEM), high-resolution TEM (HR-TEM), scanning electron microscopy (SEM), and diffuse reflectance spectroscopy (DRS). The activity of Ti3AlC2 was significantly enhanced by the integration of UV light radiation during hydrolysis. Ti3AlC2/Ti3C2Tx improved the dehydrogenation rates of NaBH4 at ambient conditions and maintained high hydrogen generation rates (HGRs) over time compared to a conventional method. It exhibited a HGR of 200–300 mL·min−1·g−1. Photo-assisted hydrolysis over the catalyst can be maintained for several times at ambient temperature. The catalyst demonstrated effective performance even after five cycles of usage.

1. Introduction

Hydrogen gas has been considered the fuel of the future [1,2]. It can be produced via several methods for hydrogen generation, such as photocatalysis [3,4,5], electrolysis [6,7,8], biological production [9], dehydrogenation of a molecule [10], and reforming of fossil fuels [11]. In general, they can classified into three common approaches: (1) thermal-based method (e.g., reforming natural gas), (2) electrolytic-based method (e.g., water electrolysis); and (3) photolytic-based method (e.g., photobiological, photoelectrochemical, and photocatalytic) [12]. However, mixed strategies were also reported, e.g., the photoelectrochemical method, which included photocatalysis and electrolysis simultaneously. Hydrogen storage is the second obstacle for the hydrogen economy after production. Hydrogen can be stored in the gas phase as a compressed gas in tanks, liquids, or solid states. Metal hydrides are promising solid-state hydrogen storage materials [13]. They offered advantages of high hydrogen capacity, require low storage pressure, and exhibit high reversibility [14,15].
MXene materials are two-dimensional (2D) metal of nitrides, carbides, or carbonitrides [16]. They have a standard formula of Mn+1XnTx (where X denotes N or C, M represents a transition metal, n equals 1-3, and Tx is surface functional groups) [17]. They are synthesized by removing the interlayer of the MAX phase. They demonstrated significant potential for various applications, including supercapacitors, photocatalysis, solar batteries, and batteries [17,18]. Among MXene materials, titanium carbide (Ti3C2) is the prototypical and most extensively studied material, and it is noted for its abundant surface active sites, high stability, and good electrical conductivity [19].
Mxene-based photocatalysts are promising for hydrogen generation via several approaches, including photocatalysis [3,20], electrocatalysis [21,22], the photoelectrochemical method [23], methane dry reforming [24], and the dehydrogenation of hydrides [25]. Thus, 2D MAX/MXene of the Ti3AlC2 monolayer and multilayers were integrated with titanium dioxide (TiO2) [26], TiO2/Ni2P [27], PtO/TiO2 [28], 1D/2D CdS [29,30], CdS/g-C3N4 [31], SrTiO3/g-C3N4 [32], metal-organic frameworks (MOFs) [33], and TiO2/MOF [34], forming heterojunctions for photocatalytic hydrogen production. They can serve as cocatalysts to improve the photocatalytic hydrogen generation of TiO2 [35]. The photocatalytic performance of MXene-based photocatalysts can be enhanced by adding noble metals [36].
Mxene also offered promising properties as a hydrogen storage material and hydrogen production from chemicals via conversion. Multilayer Ti3C2Tx MXene showed 10.47 wt.% of hydrogen storage at 25 bar and 77 K [37]. VF4/Ti3C2 improved the hydrogen storage process of Mg(BH4)2 [38]. The palladium (Pd)@MXene showed high catalytic performance in the hydrolysis of methylamine-borane (CH3NH2–BH3, MeAB) with a hydrogen generation rate of 159.4 min−1 at 318 K [39]. The Pd@Ti3AlC2 composite showed hydrogen generation from alkaline formaldehyde [40]. Pd@alkalized Ti3C2 (alk-Ti3C2) [41], Ru/Ti3C2−xNx [42], Pt/Ti3C2Tx [43], and 2D bimetallic PtyCo1−y/Ti3C2X2 [44] were reported for the hydrolysis of ammonia borane (AB). NiPt/TiO2-decorated Ti3C2Tx was reported to show hydrogen generation from hydrazine [45]. Noble metal enhanced the hydrolysis of hydrogen storage materials [46]. The photocatalytic dehydrogenation of hydrides is very limited.
Herein, the titanium aluminum carbide (Ti3AlC2) MAX phase with and without light were investigated for sodium borohydride (NaBH4) hydrolysis and hydrogen generation. The materials were characterized using X-ray diffraction (XRD), Fourier transform infrared (FT-IR), diffuse reflectance spectroscopy (DRS), Tauc’s plot, scanning electron microscopy (SEM), transmission electron microscopy (TEM), and high-resolution TEM (HR-TEM) images. UV light radiation enhanced hydrolysis in continuous high hydrogen generation rates (HGRs) compared to conventional hydrolysis (without light).

2. Results and Discussion

2.1. Characterization

Ti3AlC2 MAX materials exhibit layers of Ti-C separated with aluminum ions (Figure 1). The delamination of the material includes chemical etching using HF to remove the aluminum between the layers [47]. The material properties were identified using XRD (Figure 2a), FT-IR (Figure 2b), DRS (Figure 3a), Tauc’s plot (Figure 3b), SEM images (Figure 4a–d), TEM and HR-TEM images (Figure 5a,b).
The material crystallinity and phase purity were assessed using XRD patterns (Figure 2a). The simulated XRD pattern from JCPDS No. 52–0875 agrees with the pattern for Ti3AlC2. The XRD patterns of layered Ti3AlC2 exhibit distinct peaks at 2θ values of 9.4°, 19.1°, 33.6°, 36.6°, 38.8°, 41.5°, 44.6°, 48.1°, 52.4°, 56.5°, 60.3°, 65.5°, 72.4°, and 74.5°, corresponding to the Miller indexes of (002), (101), (103), (104), (105), (106), (107), and (108), of pristine Ti3AlC2, respectively. The diffraction peaks for Ti3AlC2 at 38.8–41.5° reveals a high degree of crystallinity (Figure 2a). HF-etching causes removing Al-layer offering multilayers of Ti3C2Tx (Figure 1).
The chemical bond and connectivity within the materials were evaluated using the FT-IR spectrum (Figure 2b). Data analysis of the FT-IR spectrum of Ti3AlC2 identifies the functional groups within the wavenumber range of 400–1000 cm−1 (Figure 2b). Al–O, Ti–O, and Ti–C vibrational modes are shown in the 400–600 cm−1 range (Figure 2b).
The optical properties of Ti3AlC2 were evaluated using DRS (Figure 3a) and Tauc’s plot (Figure 3b). There is no reflectance in the range of 400–1000 nm. On the other side, a strong reflectance was observed at 295 nm, corresponding to a bandgap of 4.2 eV using the equation of 1240/λ, where λ is the wavelength in nm, i.e., 295 nm (Figure 3b). Typical DRS values of Ti3AlC2 show no reflectance in this range. The observed reflectance could be due to the oxidation of Ti3C2Tx nanosheets into TiO2 [48,49].
Figure 4 illustrates the morphology of Ti3AlC2 as analyzed by SEM. Figure 4 illustrates the layered structure of Ti3AlC2. According to the SEM images of Ti3AlC2, the images distinctly illustrate the plate-like shape of the Ti3AlC2 particles. This observation is a distinctive attribute of MAX phase materials. The particles exhibit minor agglomeration, resulting in the formation of clusters. SEM images show a broad size distribution with a diverse range of dimensions from a few micrometers to several hundred nanometers. These observations indicate that the synthesis procedure may have produced a heterogeneous particle population. SEM analysis can be used to assess the topographical properties of the materials. The particle surfaces exhibit an exceptionally smooth texture. The particles exhibit interlocking behavior in certain regions, potentially enhancing the material’s mechanical capabilities. The SEM images indicate that the Ti3AlC2 material has a plate-like shape characterized by a broad size distribution and generally smooth surfaces.
To comprehensively understand the Ti3AlC2 material, a supplementary characterization procedure was performed using TEM (Figure 5a) and HR-TEM images (Figure 5b). TEM image depicts dark regions associated with compact stacked Ti3AlC2 (Figure 5a). However, there are also transparent objects for monolayers or a few layers of MXene materials. The particles are mildly agglomerated, creating clusters. This observation aligns with the SEM observations (Figure 4). The particles display a broad spectrum of dimensions, ranging from 50 to 200 nm. The HR-TEM image offers an enhanced resolution perspective of the material’s architecture (Figure 5b). Although the overall image seems amorphous, several areas exhibit lattice fringes, indicating the existence of nanocrystalline domains (Figure 5b).
The lattice fringes may indicate the interplanar spacing of the crystal structure. Figure 5b illustrates the interplanar distance, which is predicted to be 0.21 nm. The TEM and HR-TEM images suggest that the crystalline material confirms the XRD pattern (Figure 2).

2.2. Hydrogen Generation

Metal hydrides are promising as hydrogen storage materials. There are several metal hydrides. Among these types, NaBH4 is a renewable hydrogen storage material due to its high hydrogen capacitance of 10.6 wt.%. The hydrogen generated from NaBH4 via hydrolysis can be illustrated as NaBH4 + (2 + x)H2O → 4H2 + NaBO2·xH2O. This equation reveals that 50% of hydrogen is from NaBH4, while the other 50% comes from water molecules. The hydrolysis of NaBH4 was catalyzed using the synthesized material without and with light (Figure 6).
Hydrogen generation from NaBH4 hydrolysis is shown in Figure 6. The black line illustrates hydrogen evolution without illumination (Figure 6a). The volume of hydrogen increases consistently with time, attaining a plateau after roughly 10 min (Figure 6a). The hydrogen evolution was also recorded under illumination (Figure 6a). The hydrogen volume increased with a markedly accelerated rate relative to the dark situation, attaining a superior plateau value (Figure 6a).
The hydrogen generation rate (HGR) was plotted for experiments with and without light, as shown in Figure 6b. The y-axis denotes the HGR, defined as the hydrogen volume generated per unit time per unit mass of catalyst (mL·min−1·g−1). In the absence of light, the HGR is initially elevated but diminishes swiftly over time. Meanwhile, in the presence of light, the HGR regularly exceeds that of the dark state, signifying a substantial increase in hydrogen generation. The data unequivocally indicate that light substantially improves hydrogen evolution. This observation is demonstrated by the high hydrogen volume generated and the high HGR noted in the presence of light. The increased hydrogen production under light is due to the material’s photocatalytic activity. Light can energize electrons within the material, resulting in the formation of electron-hole pairs. Figure 6 presents evidence of the material’s photocatalytic activity and capacity to increase hydrogen production under lighting.
The recyclability of the catalyst is an essential aspect of industrial concerns. The catalytic performance of the catalyst was recycled for five cycles with and without light, as shown in Figure 7. The volume of hydrogen generated in each cycle exhibits insignificant fluctuations. This observation may result from differences in catalyst activity, reaction conditions, or reagent contaminants. There is no reduction in hydrogen generation regarding the quantity of hydrogen created. There is solely an increase in the duration needed to attain the maximum amount of hydrogen produced. The catalyst’s inherent activity is likely unaffected by repeated utilization (Figure 7). The data demonstrate that Ti3AlC2 is suitable for multiple cycles of hydrogen production via NaBH4 hydrolysis.
A summary of hydride catalysts used for hydrogen generation is tabulated in Table 1. MXene is promising for photocatalytic hydrogen production. Ti3AlC2/TiO2/Ni2P was reported for photocatalytic hydrogen generation [27]. The Ni2P cocatalyst integrated with the 2D Ti3AlC2/TiO2 composite exhibited improved visible light absorption and better charge carrier separation. The 2D Ti3AlC2/TiO2/Ni2P composite offered a maximum hydrogen generation of 13,000 μmol·g−1. It showed improved values surpassing TiO2/Ti3AlC2, TiO2/Ni2P, and pure TiO2 by factors of 1.29, 3.63, and 3.80, respectively [27]. Ti3C2Tx MXene was effectively utilized as a precursor for synthesizing C-TiO2/g-C3N4 photocatalysts without additional carbon, resulting in significantly enhanced hydrogen generation with HGR of 1409 μmol·h−1·g−1 [50]. It exhibited enhanced HGR of 8 times and 24 times higher than the HGR of pure g-C3N4 and C-TiO2, respectively. Ti3C2Tx-supported PrF3 nanosheets enhanced the dehydrogenation rates of AlH3 at low temperatures [25]. Ti3C2Tx containing 1% of PrF3 nanosheets showed a dehydrogenation capacity of 8.6% at 120 °C in 1.5 h, representing 93% of the calculated hydrogen capacity of used AlH3 [25]. Ball-milling synthesized accordion-like V2C Mxene-doped compounds in α-AlH3 [51]. V2C (1 wt.%)/α-AlH3 offered superior dehydrogenation at a low temperature of 70.5 °C with a hydrogen release capacity of 8.1 wt.%. It provided 7.8 wt.% of hydrogen within 15 min at 120 °C [51]. VF4@Ti3C2Tx improved the dehydrogenation and rehydrogenation kinetics of Mg(BH4)2 [38]. The hydrogen gas release was observed at 90 °C using VF4 (20 wt.%)@Ti3C2Tx [38]. The authors reported 8.3 wt.% higher hydrogen desorption at 275 °C [38]. A palladium-doped cryo-MXene catalyst was synthesized via a wet impregnation method [39]. After HF etching, Ti3C2Tx MXene was dropped into liquid nitrogen and kept for about 25 min at −160 °C to increase lamellar spacing, denoted as cryo-MXene. It was used for hydrogen generation via the hydrolysis of methylamine-borane. It offered a HGR of 159.4 min−1 at 318 K [39]. The hydrolysis of AB was catalyzed over PtyCo1−y/Ti3C2Tx [44]. PtyCo1−y/Ti3C2Tx showed a HGR value of 100.7 LH2 (min gPt)−1 [44]. The catalysts can be recycled based on separation via external magnets. Based on the experimental setup, hydrogen generation occurs during the in situ reduction of platinum and cobalt salts. The HGR was also calculated based on Pt. Precious metal ruthenium (Ru)-decorated TiO2 nanospheres/Ti3C2Tx were reported to catalyze the hydrolysis of NaBH4 [46]. Spherical aberration-corrected TEM analysis revealed the homogenous dispersion of Ru nanoparticles (2 nm) over TiO2. The catalyst with Ru (0.33 wt.%) loading demonstrated high catalytic efficacy in the hydrolysis of NaBH4, achieving a hydrolysis rate of 60 L·min−1·gRu−1 at 303 K [46]. The catalyst offered high HGRs but was expensive because it used precious metals such as Ru. In conclusion, the photocatalytic hydrolysis of NaBH4 using Ti3AlC2 is promising for further investigation in comparison with other catalysts, including MOFs [52,53], zeolitic imidazolate frameworks [54], and ZnO [55] (Table 1). The hydrolysis of NaBH4 is not limited to hydrogen production but can be further used for water treatment via pollutant catalytic reduction [56,57,58].

3. Experimental Section

3.1. Materials and Methods

Ti3AlC2 (purity ≥ 99%, and 40–60 μm particle size) was purchased from Advanced 2D Materials CO., Ltd., Store (China). NaBH4 was obtained from Sigma Aldrich (Germany).

3.2. Synthesis of Ti3C2Tx MXene

Ti3C2Tx was synthesized via chemical etching of Ti3AlC2 (0.5 g) in 30 mL of hydrofluoric acid solution (49%) for stirring at room temperature for 24 h [47]. The material was left for settling. It was separated and washed with water. It was redispered in water via ultrasonication until the formation of a stable colloid.

3.3. Material Characterization

XRD pattern was performed with a Philips PW1700 diffractometer (Philips, The Netherlands). The surface morphology of the catalyst samples was analyzed using ThermoFisher (USA, Quattro S Felid Emission Gun). It was also analyzed using TEM and HR-TEM with JSM-2100 (JOEL, Japan). DRS spectra were recorded using an Evolution 220 spectrophotometer (Thermo Fisher Scientific, UK), covering the wavelength range of 220 to 800 nm. FT-IR spectrum was obtained using a Nicolet model 6700 spectrophotometer (Thermo Fisher, USA) in the 400–4000 cm−1 range.

3.4. Hydrogen Generation Measurements

A 50 mL sealed photoelectrochemical cell (Corrtest®, Wuhan, China) was used to perform the catalytic reaction for NaBH4 hydrolysis. 1 mL of MXene dispersion (10 mg) was added to water (50 mL) containing 0.2 g of NaBH4. The reaction was performed at ambient temperature (25 ± 2 °C). The volume of hydrogen gas was measured using a water displacement method. The reaction was performed without and under UV-LED light (25 W, 365 nm, NICHIA, Japan).
After each cycle, the materials were recycled by adding 0.2 g of NaBH4 to the reaction cycle. The reaction was performed using the same procedure mentioned above.

4. Conclusions

This work illustrates the efficacy of Ti3AlC2 MAX/Mxene multilayers as catalysts for hydrogen production via photocatalytic NaBH4 hydrolysis. Light radiation can enhance HGR over time. The 2D MAX phase structure of the catalyst significantly enhanced its catalytic activity, facilitating hydrogen production at ambient temperature. The catalyst demonstrated exceptional stability and recyclability, preserving its efficacy across numerous cycles. The results underscore the significant potential of Ti3AlC2 MAX/MXene multilayers for practical applications in hydrogen fuel cell technology. The capacity to produce hydrogen at low temperatures and ambient settings presents considerable benefits for energy efficiency and system architecture. Continued research and development in this domain may facilitate commercializing efficient and sustainable hydrogen production techniques using MAX/MXene-based photocatalysts.

Funding

This work was supported and funded by the Deanship of Scientific Research at Imam Mohammad Ibn Saud Islamic University (IMSIU) (grant number IMSIU-DDRSP2503).

Data Availability Statement

Data is available upon reasonable request.

Conflicts of Interest

The author declare no conflict of interest.

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Inorganics 13 00044 g001
Figure 1. Chemical etching of Ti3AlC2 MAX phase.
Figure 1. Chemical etching of Ti3AlC2 MAX phase.
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Figure 2. Characterization of the materials using (a) XRD for synthesized and simulated patterns of Ti3AlC2 material and (b) FT-IR.
Figure 2. Characterization of the materials using (a) XRD for synthesized and simulated patterns of Ti3AlC2 material and (b) FT-IR.
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Figure 3. (a) DRS and (b) Tauc’s plots of prepared materials.
Figure 3. (a) DRS and (b) Tauc’s plots of prepared materials.
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Figure 4. (a–d) SEM images of Ti3AlC2 in different magnifications.
Figure 4. (a–d) SEM images of Ti3AlC2 in different magnifications.
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Figure 5. (a) TEM and (b) HR-TEM image of the material.
Figure 5. (a) TEM and (b) HR-TEM image of the material.
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Figure 6. (a) Hydrogen volume over time and (b) HGR over time for NaBH4 hydrolysis with and without light.
Figure 6. (a) Hydrogen volume over time and (b) HGR over time for NaBH4 hydrolysis with and without light.
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Figure 7. Recyclability for NaBH4 hydrolysis using Ti3AlC2 MAX/Mxene (a) without and (b) with light radiation.
Figure 7. Recyclability for NaBH4 hydrolysis using Ti3AlC2 MAX/Mxene (a) without and (b) with light radiation.
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Table 1. Summary of materials used for hydrogen generation via hydride hydrolysis.
Table 1. Summary of materials used for hydrogen generation via hydride hydrolysis.
CatalystsSynthesisHydrogen SourceHGRReaction ConditionsRef.
Pd@cryo-MXene
  • HF etching
  • Cryo-treatment
  • Reduction with NaBH4
CH3NH2-BH3159.4 min−150 mg of catalyst; 23 mg MeAB; 318 K[39]
PtyCo1−y/Ti3C2TxIn situ reduction of Pt and CoNH3BH3100.7 L H2 (min gPt)−110 mg of Ti3C2Tx; 0.115 mL of H2PtCl6 aqueous solution and CoCl2; AB (34.2 mg); 318 K[44]
Ru/TiO2/Ti3C2Tx
  • HF etching
  • Hydrothermal method, 9 h at 90 °C
  • Settling for 24 h4
  • Reduction with 5% hydrogen/argon mixture for 4 h at 573 K
NaBH460 L·min−1·gRu−10.1 g of catalyst; 5 wt.% NaOH; 1.5 wt.% NaBH4 solution; Ru loading 0.33 wt.%; 303 K[46]
Cerium-based MOFHydrothermal method1800 mLH2·gcat−1·min−150 mg catalyst; 1 g NaBH4; 333 K[52]
ZnOSol–gel method3000 mLH2·gcat−1·min−110 mg catalyst; 1 wt.% NaBH4; 303 K[55]
Ti3AlC2/Ti3C2HF etching
Ultrasonication		200–300 mLH2·gcat−1·min−1100 mg catalyst; 0.2 wt.%NaBH4; 298 K, UV-lightHerein
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Abdelhamid, H.N. Ti3AlC2 MAX/MXene for Hydrogen Generation via Photocatalytic Hydride Hydrolysis. Inorganics 2025, 13, 44. https://doi.org/10.3390/inorganics13020044

AMA Style

Abdelhamid HN. Ti3AlC2 MAX/MXene for Hydrogen Generation via Photocatalytic Hydride Hydrolysis. Inorganics. 2025; 13(2):44. https://doi.org/10.3390/inorganics13020044

Chicago/Turabian Style

Abdelhamid, Hani Nasser. 2025. "Ti3AlC2 MAX/MXene for Hydrogen Generation via Photocatalytic Hydride Hydrolysis" Inorganics 13, no. 2: 44. https://doi.org/10.3390/inorganics13020044

APA Style

Abdelhamid, H. N. (2025). Ti3AlC2 MAX/MXene for Hydrogen Generation via Photocatalytic Hydride Hydrolysis. Inorganics, 13(2), 44. https://doi.org/10.3390/inorganics13020044

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