Spatial Confinement of Pt Nanoparticles in Carbon Nanotubes for Efficient and Selective H₂ Evolution from Methanol

Abstract

H₂ generation from methanol‐water mixtures often requires high pressure and high temperature (200–300 °C). However, CO can be easily generated and poison the catalytic system under such high temperature. Therefore, it is highly desirable to develop the efficient catalytic systems for H₂ production from methanol at room temperature, even at sub‐zero temperatures. Herein, carbon nanotube‐supported Pt nanocomposites are designed and synthesized as high‐performance nano‐catalysts, via stabilization of Pt nanoparticles onto carbon nanotube (CNT), for H₂ production upon methanol dehydrogenation at sub‐zero temperatures. Therein, the optimal Pt/CNT nanocomposite presents the superior catalytic performance in H₂ production upon methanol dehydrogenation at the expense of B₂(OH)₄, with the TOF of 299.51 min^‐130 ^oC. Compared with other common carriers, Pt/CNT exhibited the highest catalytic performance in H₂ production, emphasizing the critical role of CNT in methanol dehydrogenation. The confinement of Pt nanoparticles by CNTs is conducive to inhibiting the aggregation of Pt nanoparticles, thereby significantly increasing its catalytic performance and stability. The kinetic study, detailed mechanistic insights, and density functional theory (DFT) calculation confirm that the breaking of O─H bond of CH₃OH is the rate‐controlling step for methanol dehydrogenation, and both H atoms of H₂ are supplied by methanol. Interestingly, H₂ is also successfully produced from methanol dehydrogenation at −10 °C, which absolutely solves the freezing problem in the H₂ evolution upon water‐splitting reaction.

Carbon nanotube‐supported Pt, Pd, and Rh nanocomposites (Pt/CNT, Pd/CNT, and Rh/CNT) are designed and synthesized as high‐performance nano‐catalysts, via spatial confinement of Pt, Pd, and Rh nanoparticles into CNT, for H2 production upon methanol dehydrogenation in sub‐zero temperatures.

1. Introduction

Nowadays, the world's development of economy and population experiences a rapid increase, provoking an explosive growth in energy consumption.^{[ 1} , ² , ³ , ⁴ , ^{5 ]} The excessive consumption of traditional fossil energy leads to global warming and environmental problems.^{[ 6} , ⁷ , ⁸ , ⁹ , ^{10 ]} Hence, it is highly desired to develop sustainable, green and carbon‐free energy. H₂ is deemed as the most prospective alternative for traditional fossil energy because of its high calorific value, zero‐emission, and easy accessibility.^{[ 11} , ¹² , ¹³ , ¹⁴ , ^{15 ]} In general, the industrial H₂ generation (95%) is mainly achieved by coal gasification (C + 2H₂O → CO₂ + 2H₂) and methane steam reforming (CH₄ + 2H₂O → CO₂ + 4H₂).^{[ 16} , ¹⁷ , ¹⁸ , ¹⁹ , ²⁰ , ^{21 ]} It is obvious that major H₂ generation methods rely heavily on conventional fossil fuels. This is a complete departure from the principles of the utilization of hydrogen energy.^{[ 22 ]} Additionally, the large‐scale industrial application of hydrogen is severely hampered by its safety issues as to storing and transportation, because of its extremely low density, super‐high explosibility, and liquefaction dilemma.^{[ 23 ]} Therefore, it still remains a severe challenge to develop hydrogen storage materials, including HCOOH,^{[ 24} , ²⁵ , ²⁶ , ^{27 ]} hydrazine,^{[ 28 ]} borohydrides^{[ 29} , ^{30 ]} and alcohols,^{[ 31 ]} for avoiding high cost and the safety risks in the production, storage, and transportation of hydrogen.

Methanol, which can be produced from biomass on a large scale, has been regarded as a potential hydrogen source due to its low‐cost and super‐high hydrogen density (12.5 wt.%).^{[ 31} , ³² , ³³ , ^{34 ]} In fact, H₂ generation from methanol‐water mixtures (CH₃OH + H₂O → 3H₂ + CO₂), which is also called as methanol steam reforming, has been well developed and widely used in the vehicular power generation.^{[ 35} , ³⁶ , ^{37 ]} Homogeneous catalysts for H₂ production from methanol are developed for ages, but they exhibited poor activity and selectivity.^{[ 38 ]} Indeed, some low molecular weight organic matter (such as acetic acid,^{[ 39 ]} formaldehyed,^{[ 40 ]} formate salts,^{[ 41 ]} methyl formate^{[ 42 ]} and dimethyl acetal^{[ 43 ]}) were obtained as by‐products, greatly decreasing the efficiency of methanol steam reforming.^{[ 44 ]} So this reaction, which is typically catalyzed by heterogeneous catalysts, often requires high pressure and high temperature (200–300 °C).^{[ 45 ]} However, CO can be easily generated and poison the catalytic system of fuel cell, as well as contaminate the H₂ gas under such high temperature.^{[ 46} , ^{47 ]} Therefore, it is highly desirable to develop the efficient catalytic systems for H₂ production from methanol at much lower temperature.^{[ 48} , ⁴⁹ , ^{50 ]} For example, Zhou's group first reported [Cp*IrCl(phen)]Cl catalyzed H₂ generation from methanol at near‐room temperature.^{[ 51 ]} Herein, we have first reported carbon nanotube‐supported Pt, Pd, and Rh nanocomposites (Pt/CNT, Pd/CNT, and Rh/CNT) as high‐performance nanocatalysts, via stabilization of Pt, Pd, and Rh nanoparticles onto carbon nanotube (CNT),^{[ 52} , ⁵³ , ^{54 ]} for H₂ production upon methanol dehydrogenation at 30 °C (Equation 1). Therein, the optimal Pt/CNT nanocomposite presented the superior catalytic activity in H₂ evolution upon methanol dehydrogenation at the expense of B₂(OH)₄, with a TOF value of 299.51 min⁻¹ at 30 °C. Among them, B₂(OH)₄ was frequently applied in borylation reaction and reduction reaction,^{[ 22 ]} and recently used as the sacrificial agent for H₂ production.^{[ 55} , ^{56 ]} In order to speculate and verify its mechanism, the carrier effect, kinetic study, kinetic isotope effect, tandem reaction, and density functional theory (DFT) of H₂ production upon methanol dehydrogenation had been scrutinized in detail. Interestingly, H₂ was also successfully produced from methanol dehydrogenation at −10 °C, which absolutely solved the freezing problem in the H₂ evolution upon water‐splitting reaction.

$$2\mathrm{MeOH}+{\mathrm{B}}_2{(\mathrm{OH})}_4\to 2\mathrm{MeOB}{(\mathrm{OH})}_2+{\mathrm{H}}_2\uparrow$$ (1)

2. Results and Discussion

2.1. The Methanol Dehydrogenation Catalyzed by Different Nanocomposites

As demonstrated in Scheme  1 , Pt/CNT, Pd/CNT, and Rh/CNT were prepared by using metal salts (including PtCl₄, K₂PdCl_4, and Rh(NO₃)₃) and CNT, followed by NaBH₄ reduction in H₂O at 30 ^oC, respectively. Then catalytic activities of Pt/CNT, Pd/CNT, and Rh/CNT for H₂ production upon methanol dehydrogenation at the expense of B₂(OH)₄ were recorded in Figure  1a. The result exhibited that Pt/CNT showed a much higher TOF (299.51 min⁻¹) than those of Pd/CNT (41.85 min⁻¹) and Rh/CNT (26.52 min⁻¹) in H₂ production upon methanol dehydrogenation. Next, some common carriers, including CeO₂, ZrO₂, NiO, ZnO, Fe₃O₄, and CoFe₂O₄, had also been measured for methanol dehydrogenation. Pt/CeO₂ (Figure S1, Supporting Information), Pt/ZrO₂ (Figure S2, Supporting Information), Pt/NiO (Figure S3, Supporting Information), Pt/ZnO (Figure S4, Supporting Information), Pt/Fe₃O₄ (Figure S5, Supporting Information) and Pt/CoFe₂O₄ (Figure S6, Supporting Information) nanocomposites were obtained at standard condition. As displayed in Figure 1b, the order of TOF value in H₂ production follows: Pt/CNT (299.51 min⁻¹) > Pt/CeO₂ (200.28 min⁻¹) > Pt/ZrO₂ (133.17 min⁻¹) > Pt/NiO (27.90 min⁻¹), whereas Pt/ZnO, Pt/Fe₃O₄ and Pt/CoFe₂O₄ were catalytically inactive (Figure S7, Supporting Information). In summary, Pt/CNT exhibited the superior TOF value of 299.51 min⁻¹ in H₂ production, emphasizing the critical role of CNT in methanol dehydrogenation. It seems that the confinement of Pt nanoparticles by CNTs is conducive to inhibiting the aggregation of Pt nanoparticles, thereby significantly increasing its catalytic performance and stability.

Scheme 1.

The synthesis of Pt/CNT.

Figure 1.

H₂ evolution catalyzed by a) Pt/CNT, Pd/CNT, and Rh/CNT; b) Pt/CoFe₂O₄, Pt/Fe₃O₄, Pt/ZnO, Pt/NiO, Pt/ZrO₂, Pt/CeO₂, and Pt/CNT. Reaction condition: B₂(OH)₄ (2 mmol), catalyst (0.2 mol.%), and MeOH (2 mL).

2.2. Characterization of Pt/CNT

As illustrated in Figure  2a, the BET result presented the BET surface area, total pore volume and mean pore diameter of Pt/CNT nanocomposite is 97.64 m² g⁻¹, 0.47 cm³ g⁻¹, and 19.08 nm, respectively, indicating that Pt/CNT possessed a mesoporous structure.^{[ 57 ]} A distinct characteristic peak at 26^o, which is corresponding to graphene (002) (JCPDS card No. 75‐1621), was recorded in Figure 2b.^{[ 58 ]} The distinct peaks of Pt (311), Pt (220), Pt (200), and Pt (111) at 81.5^o, 68.1^o, 46.7^o resp. 39.8^o were recorded in XRD, indicating that PtNPs were stabilized onto CNT (JCPDS card No. 65‐2868).^{[ 59 ]} Next, the Pt content of Pt/CNT was measured by ICP to be 4.46 wt.%, which is just slightly lower than the theoretical value (4.65 wt.%). The obvious peaks of D‐band (1383.02 cm⁻¹), G‐band (1584.86 cm⁻¹) and 2D‐band (2758.13 cm⁻¹) were observed in Figure 2c.^{[ 60 ]} Among them, the G‐band and D‐band were corresponding to graphite carbon resp. disordered carbon. The small value of I _D/I _G (0.27) illustrated that there were only few crystal defects in Pt/CNT. The external nano‐structure and nano‐morphology Pt/CNT nanocomposite had also been measured by TEM and HRTEM. As illustrated in Figure 2d,e, Pt/CNT nanocomposite possessed a nanotube structure. Some Pt nanoparticles (3.79 nm, Figure S8, Supporting Information) were located at the surface of CNT, other Pt nanoparticles were encapsulated into CNT. C (002), where its crystal lattice spacing is 0.33 nm, was recorded in the exterior (Figure 2f). While Pt (111) of 0.23 nm was presented at the interior, further confirming some Pt nanoparticles were encapsulated into CNT.^{[ 61 ]} Moreover, the precise localization of C, N, O, and Pt elements in Pt/CNT nanocomposite had been further characterized by EDX. As shown in Figure  3 , the surface of Pt/CNT was consisted of Pt, O, N, and C elements. It is obvious that some Pt nanoparticles were confined into CNT. This confinement of Pt nanoparticles by CNTs is conducive to inhibiting the aggregation of Pt nanoparticles, thereby significantly increasing its catalytic performance and stability.^{[ 62} , ⁶³ , ^{64 ]}

Figure 2.

a) BET, b) XRD, c) Raman spectrum, d,e) TEM, and f) HRTEM of Pt/CNT.

Figure 3.

a) STEM, b) combined Pt, O, N, and C, c) Pt, d) O, e) N, and f) C EDX mapping of Pt/CNT.

In addition, the chemical valence states of surface elements of Pt/CNT had also been determined by XPS in Figure  4a. The high‐resolution Pt 4f_7/2 spectrum of Pt/CNT was divided into two peaks at 71.63 and 72.71 eV, which were attributed to Pt (0) (74.38%) resp. Pt (II) (25.63%) species (Figure 4b).^{[ 65 ]} This result had indicated that Pt (0) was partly oxidized to Pt (II) by O₂. As illustrated in Figure 4c, the C 1s spectrum was decomposed into three characteristic peaks of C sp² at 284.78 eV and C sp³ at 285.61 eV, respectively.^{[ 66 ]} As shown in Figure 4d, the O 1s spectrum of Pt/CNT nanocomposite was divided into two typical peaks of 531.88 and 533.52 eV, assigned to C═O and C─O, respectively.^{[ 67 ]} These O‐containing functional group in CNTs could protect the Pt nanoparticles by enhancing its stability and decreasing the leaching of Pt in the confined space. In addition, the XPS of Pt/ZrO₂ was also measured in Figure S9 (Supporting Information), a slight shift was found in Pt 4f of Pt/CNT as compared to Pt 4f of Pt/ZrO₂, suggesting the electron transfer from Pt atom into CNT surface. Thus, the superior catalytic performance of Pt/CNT in methanol dehydrogenation might be ascribed to its electronic interaction effect and synergistic effect.^{[ 68 ]}

Figure 4.

a) sum spectrum, b) Pt 4f, c) C 1s, and d) O 1s XPS of Pt/CNT.

In order to further identify the coordination and valence states of Pt/CNT, X‐ray absorption near edge structure (XANES) spectra of the Pt L3‐edge over Pt/CNT catalyst, Pt foil, PtO, and PtO₂ had been performed in Figure  5a. the green peak of Pt/CNT was lower than that of PtO and slightly higher than that of Pt foil reference, suggesting the chemical charge of Pt atoms in Pt/CNT is between 0 and +2.^{[ 69 ]} Then, the Fourier transform extended X‐ray absorption fine structure (FT‐EXAFS) spectra of Pt/CNT uncovered that the presence of Pt–Pt, Pt–O–Pt, and Pt–C/O coordinations (Figure 5b,c),^{[ 70} , ^{71 ]} demonstrating that Pt nanoparticles had been successfully stabilized by CNT. As shown in Figure 5d, the presence of Pt–Pt and Pt–C/O coordinations was also confirmed by wavelet transformed XAS analysis.^{[ 72 ]} In Table S1 (Supporting Information), the coordination configurations of Pt atoms in Pt/CNT were measured by quantitative least‐squares EXAFS best‐fitting analysis. The coordination number of Pt–C/O, Pt–Pt, and Pt–O–Pt was 1.6, 4.8, and 2.0, respectively. In summary, these results further confirmed that chemical charge of Pt atoms in Pt/CNT is between 0 and +2, which was in line with XPS.

Figure 5.

a) XANES spectra of the Pt L3‐edge over the Pt/CNT catalyst, Pt foil, PtO, and PtO₂; b) FT‐EXAFS spectra of Pt/CNT catalyst, Pt foil, PtO, and PtO₂; c) EXAFS k space fitting curves of Pt/CNT catalyst, Pt foil, PtO, and PtO₂; d) Wavelet transformed XAS signal of Pt/CNT.

2.3. Kinetic Study

The kinetic study (such as B₂(OH)₄ dosage, Pt/CNT amount, and reaction temperature) of H₂ production upon methanol dehydrogenation at the expense of B₂(OH)₄ was further studied in detail. First, the H₂ production catalyzed by 0.2 mol.% Pt/CNT was conducted in the various B₂(OH)₄ amounts from 1.0 to 2.5 mmol at MeOH (2 mL). In Figure  6a, the H₂ production rate was independent of B₂(OH)₄ amounts, suggesting H₂ production was a zero‐order reaction in B₂(OH)₄ concentration. In general, 1 mol of H₂ was generated upon the expense of 1 mol of B₂(OH)₄. While the H₂ production rate boosted with the increment of Pt/CNT concentration (Figure 6b), with the slope was 1.67, indicating H₂ production was a first‐order reaction in Pt/CNT concentration. In order to obtain E _a of H₂ production upon methanol dehydrogenation over Pt/CNT, the methanol dehydrogenation was conducted from 273 to 303 K (Figure 6c). Based on the Arrhenius law, the E _a was found to 19.59 kJ mol⁻¹. Then other common alcohols, including ethanol and propanol, had also been tested for H₂ production. As described in Figure 6d, H₂ was also successfully generated from ethanol (207.37 min⁻¹) and propanol (123.84 min⁻¹), but it needed 2.5 and 8 min induction time, respectively. Interestingly, H₂ was also successfully produced from methanol dehydrogenation at −10 °C (Figure 6e), which absolutely solved the freezing problem in the H₂ evolution upon water‐splitting reaction.

Figure 6.

Plots of obtained H₂ volume versus time for H₂ evolution from MeOH with a) different concentrations of B₂(OH)₄, b) various amounts of Pt/CNT, c) various reaction temperatures; d) CH₃OH, C₂H₅OH and C₃H₇OH, e) at 263 K, f) Stability test on the Pt/CNT catalyst in H₂ evolution.

2.4. Stability of Pt/CNT Nanocomposite

It is also vital to demonstrate the stability of Pt/CNT in H₂ production upon methanol dehydrogenation at the expense of B₂(OH)₄ for the further industrial and practical application. As described in Figure 6f, the result confirmed that Pt/CNT still kept excellent H₂ production rate after at least five runs in methanol dehydrogenation. Then, the 5^th recycled Pt/CNT nanocomposite was further measured by TEM and XPS. Figure S10 (Supporting Information) exhibited the size of 5^th recycled Pt/CNT nanocomposite (3.92 nm, Figure S11, Supporting Information) kept the same as fresh one (3.79 nm). In Figure S12 (Supporting Information), the contents of Pt (II) and Pt (0) of 5^th recycled Pt/CNT also remained the same as the fresh one. Indeed, H₂ production rate remained unchanged after five times recycling of Pt/CNT, suggesting that Pt/CNT nanocomposite was an excellent stable, heterogeneous, and recyclable nanocatalyst for methanol dehydrogenation. Moreover, the commercial Pt/C was also tested for H₂ production upon methanol dehydrogenation. Although commercial Pt/C was as efficient as Pt/CNT in H₂ production upon methanol dehydrogenation at first, the catalytic activity of Pt/C greatly deceased after five runs in methanol dehydrogenation Figure S13 (Supporting Information). According to TEM pictures, we found the size of 5^th recycled Pt/C had increased from 3.77 (Figures S14,S15, Supporting Information) to 5.15 nm (Figures S16,S17, Supporting Information). More importantly, H₂ production rate still remained unchanged after ten times recycling of Pt/CNT (Figure S18, Supporting Information). In summary, the confinement of Pt nanoparticles by CNTs is conducive to inhibiting the aggregation of Pt nanoparticles, thereby significantly increasing its catalytic performance and stability.

2.5. The Mechanism of Methanol Dehydrogenation

H₂ production upon methanol dehydrogenation was performed in CH₃OH resp. CD₃OD was recorded in Figure  7a. A large KIE of 2.22 was obtained indicating that the breaking of O─H bond of MeOH is the rate‐controlling step for methanol dehydrogenation.^{[ 73 ]} In Figure 7b, the gas mixture obtained from methanol dehydrogenation was confirmed by gas chromatograms (GC) to be only H₂, illustrating that H₂ generation upon methanol dehydrogenation over Pt/CNT has been successfully realized towards fuel cell power systems.

Figure 7.

a) H₂ evolution from MeOH catalyzed by Pt/CNT in CD₃OD (red) or CH₃OH (blue); b) GC spectra of evoluted gas mixture from MeOH over Pt/CNT at 30 °C.

H₂ generation upon methanol dehydrogenation is not only applied in the safe and efficient generation, storage, and transportation of H₂, but also in its in situ tandem reactions. As shown in Figure S19 (Supporting Information), tandem reaction was carried out in a dual‐chamber reactor for 1,1‐diphenylethylene hydrogenation with in situ produced H₂ from methanol dehydrogenation, and the target product of 1,1‐diphenylethane was provided in > 99% yield, which was confirmed by ¹H‐NMR (Figure S20, Supporting Information). In addition, the by‐production of B(OH)₂OMe was further identified by mass spectrum (Figure S21, Supporting Information) and ¹H‐NMR (Figure S22, Supporting Information). As shown in Figure  8 , D₂ was successfully generated from CD₃OD dehydrogenation, then deuterated 1,1‐diphenylethane was also obtained in > 99% yield, which was confirmed by ¹H‐NMR (Figure S23, Supporting Information). The formation of Ph₂CD‐CH₂D was also verified by mass spectrum (Figure S24, Supporting Information). These result suggested both H atoms of H₂ are supplied by CH₃OH.

Figure 8.

Tandem reaction for 1,1‐diphenylethylene hydrogenation using D_2.

2.6. DFT Calculation

To further verify the mechanism of H₂ generation upon methanol dehydrogenation, the systematic DFT calculation was also performed. According to our previous work,^{[ 74 ]} Pt₁₈ clusters and methanol were chosen as models for H₂ generation upon methanol dehydrogenation, the plausible mechanism pathway and energy change of H₂ generation upon methanol dehydrogenation were concluded in Figure  9 . First, B₂(OH)₄ was adsorbed on Pt₁₈ clusters to give I, the bond length of B‐B bond was enhanced from 1.724 to 3.502 Å (green line), indicating B─B bond was completely disconnected. 32 kcal mol⁻¹ energy was released, suggesting that this reaction was spontaneous. Subsequently, H₂ and MeOB(OH)₂ were formed, via TS (II) (H─H bond length and B─H bond length are 1.372 Å resp. 1.451 Å), by the reaction of B₂(OH)₄ and methanol at the surface of Pt₁₈ cluster (H─H bond length and B─H bond length are 2.893 Å resp. 1.496 Å). The gradual shortening of the H─H (orange dotted line) and B─H (purple dotted line) bond lengths had proved the formation of H₂ and MeOB(OH)₂. The activation energy (∆E1) and energy difference (∆E2) were 32.7 and −69.8 kcal mol⁻¹, respectively, suggesting our speculative mechanism is feasible.

Figure 9.

Relative electronic energy (blue) diagram for H₂ generation over Pt/CNT.

Based on our control experiments, tandem reaction and DFT calculation, the feasible mechanism of methanol dehydrogenation was proposed in Figure  10 . First, B₂(OH)₄ reacted with Pt/CNT to give intermediate I, being subsequently converted into intermediate II by the attack of MeOH molecules. The large KIE of 2.22 indicated that the breaking of O─H bond of MeOH was the rate‐controlling step for methanol dehydrogenation. Finally, Pt(H)₂ species III was generated from intermediate II by releasing MeOB(OH)₂, simultaneously providing H₂.

Figure 10.

The proposed mechanism of H₂ generation upon methanol dehydrogenation.

3. Conclusion

In summary, a sequence of carbon nanotube‐supported Pt, Pd, and Rh nanocomposites (Pt/CNT, Pd/CNT, and Rh/CNT) have been designed and synthesized as high‐performance nano‐catalysts, via stabilization of Pt, Pd, and Rh nanoparticles onto CNT, for H₂ production upon methanol dehydrogenation. Therein, the optimal Pt/CNT presented the superior catalytic activity in H₂ production upon methanol dehydrogenation at the expense of B₂(OH)₄, with a TOF value of 299.51 min⁻¹ at 30 °C. Compared with other common carriers, including CeO₂, ZrO₂, NiO, ZnO, Fe₃O₄, and CoFe₂O₄, Pt/CNT exhibited the superior catalytic performance in H₂ evolution, emphasizing the critical role of CNT in methanol dehydrogenation. The confinement of Pt nanoparticles by CNTs is conducive to inhibiting the aggregation of Pt nanoparticles, thereby significantly increasing its catalytic performance and stability. The kinetic study (including Pt/CNT concentration, B₂(OH)₄ amount, and dehydrogenation temperature) and detailed mechanistic insights, particularly KIE test, tandem reaction, GC result, and DFT calculation, confirmed that the breaking of O─H bond of MeOH was the rate‐controlling step for methanol dehydrogenation, and both H atoms of H₂ were supplied by CH₃OH. Interestingly, H₂ was also successfully produced from methanol dehydrogenation at −10 °C, which absolutely solved the freezing problem in the H₂ evolution upon water‐splitting reaction.

A drawback of H₂ production upon methanol dehydrogenation is the difficulty of regenerating B₂(OH)₄ from MeOB(OH)₂, but this challenge is also appropriate for the other hydroborons.^{[ 75 ]} Further study about the regeneration of B₂(OH)₄ from MeOB(OH)₂ is currently under investigation in our group.

This work not only develops an efficient catalytic system for H₂ production from methanol in sub‐zero temperatures, but it also proposes an easy and simple method for pure D₂ production upon CD₃OD dehydrogenation.

Conflict of Interest

The authors declare no conflict of interest.

Supporting information

Supporting Information

Jin X., Yan J., Liu X., Zhang Q., Huang Y., Wang Y., Wang C., Wu Y., Spatial Confinement of Pt Nanoparticles in Carbon Nanotubes for Efficient and Selective H₂ Evolution from Methanol. Adv. Sci. 2024, 11, 2306893. 10.1002/advs.202306893

Data Availability Statement

The data that support the findings of this study are available from the corresponding author upon reasonable request.