Photocatalytic aerobic oxidation of C(sp3)-H bonds

Zhang, Lei; Li, Run-Han; Li, **ao-**n; Wang, Shengyao; Liu, Jiang; Hong, **ao-Xuan; Dong, Long-Zhang; Li, Shun-Li; Lan, Ya-Qian

doi:10.1038/s41467-024-44833-y

Photocatalytic aerobic oxidation of C(sp³)-H bonds

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Published: 15 January 2024

Volume 15, article number 537, (2024)
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Photocatalytic aerobic oxidation of C(sp³)-H bonds

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Abstract

In modern industries, the aerobic oxidation of C(sp³)-H bonds to achieve the value-added conversion of hydrocarbons requires high temperatures and pressures, which significantly increases energy consumption and capital investment. The development of a light-driven strategy, even under natural sunlight and ambient air, is therefore of great significance. Here we develop a series of hetero-motif molecular junction photocatalysts containing two bifunctional motifs. With these materials, the reduction of O₂ and oxidation of C(sp³)-H bonds can be effectively accomplished, thus realizing efficient aerobic oxidation of C(sp³)-H bonds in e.g., toluene and ethylbenzene. Especially for ethylbenzene oxidation reactions, excellent catalytic capacity (861 mmol g cat⁻¹) is observed. In addition to the direct oxidation of C(sp³)-H bonds, CeBTTD-A can also be applied to other types of aerobic oxidation reactions highlighting their potential for industrial applications.

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Introduction

In industrial oxidation processes with a demand of >1000 tons/annum listed in Ullmann’s Encyclopedia of Industrial Chemistry, the direct oxidation of C(sp³)–H bonds using O₂ as an oxidant agent accounts for a significant proportion (49 examples of 109 total examples)^1,2. The obtained products have a wide range of applications in the pharmaceutical and fine chemical industries^{Full size image}

Transient absorption spectra (TAS) tests were performed to determine the process of photoexcitation and excited state species generation of each component in CeBTTD-A (Fig. 5b, c), which can help to analyze the transition mode of photogenerated charges. The positive excited state absorption (ESA) bands of 9-AC and negative ground-state bleaching (GSB) peak of CeBTTD-A at 550 nm can explain that the photogenerated electrons of 9-AC can quickly migrate to other motifs in CeBTTD-A (Supplementary Fig. 28). The negative stimulated emission in H₄BTTD at 650 nm is weakened in CeBTTD-A, indicating that the photoelectrons from 9-AC are transferred to BTTD⁴⁻. The unchanged electron density of Ce ions determined by in situ XPS under light irradiation showed that Ce ions do not receive photoelectrons (Supplementary Fig. 29). The positive ESA bands at 1100 nm show that the lifetime of excited state 9-AC is much longer than BTTD⁴⁻ and CeBTTD-A, which is in line with the analysis of kinetic processes probed at 1100 nm^29,30. It also proves that the migration direction of the photoelectron is from 9-AC to BTTD⁴⁻. Density functional theory (DFT) theoretical calculations were performed to better understand the photogenerated charge separation and migration process of CeBTTD-A under illumination. As shown in Supplementary Fig. 30, the main vertical excitations of CeBTTD-A under illumination occur at 397, 412, 415, 484, and 547 nm. The attribution of the electron transition indicates that the excitation near 400 nm is mainly contributed by the transition of 9-AC itself (Supplementary Table 12), which is consistent with the absorption spectrum of 9-AC (Fig. 3a). Among them, the major contributions at 397, 412, and 484 nm are the electrons in HOMO-1 of 9-AC excited to other orbits (LUMO + 4, LUMO + 2 and LUMO + 1 respectively, Supplementary Fig. 31). It means that the hole located in HOMO-1 with higher energy than HOMO can be the major part involving the toluene C–H bond oxidation. Combined with the XAS characterization results, a reasonable photogenerated charge separation and transition process was proposed (Fig. 5d). Firstly, some electrons located in different orbits of 9-AC and BTTD motifs are excited and generate corresponding BTTD* and 9-AC* excited species under illumination. Subsequently, the excited photoelectrons of 9-AC* are transferred to BTTD*, forming 9-AC^•+ and BTTD^•ˉ. The photogenerated holes located in the inner orbits of 9-AC complete the oxidation of the C-H bonds, and the electrons on BTTD complete the O₂-to-O₂^•ˉ reduction and finally achieve the oxidation of C(sp³)–H bonds.

In addition to the aerobic oxidation of C(sp³)–H bonds, we broaden our testing to other photocatalytic aerobic reactions, such as benzyl alcohol oxidation, anisole oxidation, and benzylamine oxidative coupling reactions to assess the universal applicability of CeBTTD-A. As shown in Fig. 6a–c, all these aerobic reactions demonstrated excellent photocatalytic performance and good substrate tolerance. These promising results encourage us to perform the five photocatalytic oxidation reactions mentioned in this paper in outdoor sunlight and ambient air. When the reactions were executed under real sunlight on October 10–12, 2022 (Guangzhou, China), the oxidation reactions could still be completed after 8-h illumination (Fig. 6d). Different from the results of indoor laboratory reactions, the product of the oxidation of thioanisole was mainly methyl phenyl sulfoxide, which is probably caused by the shorter duration of illumination (Fig. 6e) than indoor laboratory condition. This highly efficient photocatalytic system driven entirely by sunlight and air without any additional cost further demonstrated the advantages and commercial potential of CeBTTD-A.

**Fig. 6: Photocatalytic performance in other photocatalytic aerobic reactions and sunlight- and ambient air-driven aerobic oxidation reactions.**

In summary, we designed and developed a hetero-motif molecular junction as a model photocatalyst applied to photocatalytic aerobic oxidation of C(sp³)–H bonds. Benefited from the strong π-π interaction between the motifs in the molecular junction structure, the constructed photocatalyst CeBTTD-A can undergo rapid intermolecular migration of photogenerated charges and substrate (O₂ and C(sp³)-H bonds) activation under light irradiation, so as to achieve high reactivity for oxidation of toluene and ethylbenzene derivatives. A solvent-free ten-gram-scale reaction of ethylbenzene oxidation under ambient air could be fully accomplished, which reveals better performance than other photo- or thermal-driven catalytic systems reported up to now. Apart from C(sp³)-H bond oxidation reactions, CeBTTD-A can also be applied to three other kinds of general aerobic reactions and also exhibit excellent reaction activities. More importantly, all these aerobic reactions can be driven entirely by sunlight and air without additional energy or cost input, which reveals the commercialized application prospect. We anticipate that our operating principles of hetero-motif molecular junction photocatalyst will provide inspiration to develop next-generation photocatalysts for widespread applications in constructing complex molecular blocks and break the bottleneck of sunlight- and ambient air-driven photocatalysis of more challenging reactions in an atom-economic and environment-friendly and sustainable way.

Methods

Synthesis

All starting materials, reagents, and solvents used in experiments were commercially available, high-grade purity materials and used without further purification.

Preparation of H₄BTTD

N,N-Bis(3,5-Dicarboxyl)-1,6,7,12-Tetrachloroperylene-3,4,9,10-Tetracarboxylic Diimide (H₄BTTD, BTTD in the manuscript represents the deprotonated ligand): In a 50 mL single necked flask, a mixture of 3,5-dibromoaniline (3.0 g, 12.0 mmol), 1,6,7,12-Tetrachloroperylene Tetracarboxylic Acid Dianhydride (1.0 g, 2.0 mmol) and propanoic acid (25.0 mL) was heated in 160 °C with a reflux condenser and a magnetic stirring bar for 48 h. After the reaction, the organic solvent was removed, and the precipitate was collected under reduced pressure at room temperature. Wash the precipitate with plenty of water and a small amount of ethanol to remove residual propionic acid. The crude product was dried in a vacuum oven at 60 °C for 9 h, and red powder H₄BTTD was obtained as pure product (yield 80% based on dianhydride). ¹H-NMR (400 MHz, D₆-DMSO): δ = 8.30 (d, ³J = 1.6 Hz, 4H, CH), 8.60 (t, ³J = 1.6 Hz, 2H, CH), 8.64 (s, 4H, CH) ppm.

Preparation of Ce₆

Ce₆O₄(OH)₄(NH₃CH₂COO)₈(NO₃)₄(H₂O)₆Cl₈·8H₂O: Ce₆ is prepared based on previous reports with slight modifications³¹. Ammonium cerium nitrate (30.0 g, 54.7 mmol) and glycine (9.0 g, 120.0 mmol) were dissolved in 30.0 mL ultrapure water to obtain an orange solution. Then, the solution was added to 270.0 mL of a saturated sodium chloride solution. Then, the obtained yellow solution was placed at 25 °C for a week, and the solids were filtered and collected. The solid was washed with a small amount of ice water solution several times to remove the excessive glycine and sodium chloride. The crude product was dried in a vacuum oven in 60 °C for 5 h, and the light-yellow solid Ce₆ was obtained (70% based on ammonium cerium nitrate).

Preparation of CeBTTD-B

Ce₂BTTD(C₆H₅COO)₂(H₂O)₄: 30 mg Ce₆, 5 mg H₄BTTD, 20 mg Benzoic acid (BA for short), and 3 mL DMF were charged in a 10 mL pressure-resistant glass tube and heat at 150 °C for 72 h. After cooling down to room temperature, orange single crystals of CeBTTD-B were collected (85% based on H₄BTTD).

Preparation of CeBTTD-N

Ce₂BTTD(C₁₀H₉COO)₂(H₂O)₄: 30 mg Ce₆, 5 mg H₄BTTD, 20 mg 1-naphthoic acid (NA for short) and 3 mL DMF were charged in a 10 mL pressure-resistant glass tube and heat at 150 °C for 72 h. After cooling down to room temperature, brown single crystals of CeBTTD-N were collected (70% based on H₄BTTD).

Preparation of CeBTTD-A

Ce₂BTTD(9-AC)₂(DMF)₂(H₂O)₂: 30 mg Ce₆, 5 mg H₄BTTD, 20 mg 9-anthroic acid (9-AC for short), and 3 mL DMF were charged in a 10 mL pressure-resistant glass tube and heat at 150 °C for 72 h. After cooling down to room temperature, dark brown single crystals of CeBTTD-A were collected (80% based on H₄BTTD).

Single-crystal X-ray diffraction

Single-crystal X-ray intensity data collection for CeBTTD crystals was carried out at 150 K with a Bruker D8 Venture diffractometer equipped with a PHOTON III detector using the monochromatized wavelength (Cu Kɑ) = 1.54178 Å. The crystal structures were solved and refined by full-matrix least-squares methods against F² using the SHELXL-2014 program package^32,33 and Olex-2 software³⁴. All non-hydrogen atoms were refined with anisotropic displacement parameters, and hydrogen positions were fixed at calculated positions and refined isotropically. The topological analysis was performed with the TOPOS program³⁵. The crystallographic data and structure refinement for CeBTTD crystals are summarized in Supplementary Table 1. The selected bond lengths and bond angles of CeBTTD-B, CeBTTD-N, and CeBTTD-A are listed in Supplementary Tables 2–7, respectively.

Due to the small size of CeBTTD-B and CeBTTD-N crystals, the diffraction intensity was weak, resulting in low resolution and low bond precision on C–C bonds. The B-level alerts of “D–H bond without acceptor” can be explained that the acceptor might be the free solvent molecules squeezed. Although there are some problems in these X-ray analyses, we think that these results can strongly support the determination of the structure of CeBTTD coordination polymers and the discussion about the bond lengths and angles.

Analytical techniques

Thermogravimetric analysis (TGA) of the sample was performed on a Perkin-Elmer TG-7 analyzer heated from room temperature to 800 °C in flowing N₂/O₂ with a heating rate of 10 °C/min. Fourier transform infrared spectroscopy (FTIR) was recorded in the range of 4000–400 cm⁻¹ on a Mattson Alpha-Centauri spectrometer using the technique of pressed KBr pellets. Powder X-ray diffraction (PXRD) measurements were recorded ranging from 5 to 50° at room temperature on a D/max 2500 VL/PC diffractometer (Japan) equipped with graphite mono-chromatized Cu Kα radiation (λ = 1.54060 Å)²⁴. The UV–visible diffuse reflection spectra were acquired on a Shimadzu UV-2550 spectrophotometer in the wavelength range of 300–800 nm. X-ray photoelectron spectroscopy (XPS) was measured on an Escalab 250**. In situ electron paramagnetic resonance (EPR) spectra were recorded on a Bruker A300 spectrometer. Electrochemical measurements (photocurrent and the Mott–Schottky spots) were carried out using an electrochemical workstation CHI 660E. The products of the aerobic oxidation reaction were detected and analyzed by gas chromatography-mass spectrometer (GC–MS, 8890-5977B, Agilent), gas chromatography (GC, 8890, Agilent), and nuclear magnetic resonance (¹H NMR, Varian VNMRS).

The femtosecond transient absorption setup used for this study is based on a regenerative amplified Ti:sapphire laser system from Coherent (800 nm, 35 fs, 6 mJ pulse-1, and 1 kHz repetition rate), nonlinear frequency mixing techniques and the Femto-TA100 spectrometer (Time-Tech Spectra). Briefly, the 800 nm output pulse from the regenerative amplifier was split into two parts with a 50% beam splitter. The transmitter part was used to pump a TOPAS Optical Parametric Amplifier (OPA), which generates a wavelength-tunable laser pulse from 250 nm to 2.5 μm as a pump beam. The reflected 800 nm beam was split again into two parts. One part with less than 10% was attenuated with a neutral density filter and focused into a 2 mm thick sapphire window to generate a white light continuum (WLC) from 420 nm to 800 nm used for the probe beam. The probe beam was focused with an Al parabolic reflector onto the sample. After the sample, the probe beam was collimated and then focused into a fiber-coupled spectrometer with CMOS sensors and detected at a frequency of 1 kHz³⁶. The delay between the pump and probe pulses was controlled by a motorized delay stage. The pump pulses were chopped by a synchronized chopper at 500 Hz, and the absorbance change was calculated with two adjacent probe pulses (pump-blocked and pump-unblocked). Nanosecond TA measurement was performed with the EOS spectrometer (Ultrafast Systems LLC). The pump beam is generated in the same way as the femtosecond TA experiment described above. A different white light continuum (380–1700 nm, 0.5 ns pulse width, 20 kHz repetition rate) was used, which was generated by focusing a Nd:YAG laser into a photonic crystal fiber. The delay time between the pump and probe beam was controlled by a digital delay generator (CNT-90, Pendulum Instruments)³⁷.

Photocatalysis activity measurement

Before the catalytic tests, the single crystal of CeBTTD-(B/N/A) was washed with DMF and ethanol in turn and then heated at 60 °C for 4 h in a vacuum oven.

Three milliliter CH₃CN (GR) and 5 mg catalysts are placed in a 50 mL quartz tube. A flow rate of 0.1 L/min for 5 min under the gas (high pure N₂/O₂ > 99.995%) to ensure that the air in the reaction system was completely exchanged (when the atmosphere is ambient air, this step is omitted). Then, 0.1 mmol substrate was quickly added to the tube under the gas flow. A 300 W Xenon lamp (light intensity: 200 mW cm⁻², λ = 300–1100 nm) was used as the light source. The reaction temperature was controlled at 298 K by using the cooling water circulation. After the reaction, the solution was collected, centrifuged, and filtered through a 0.22 μm syringe filter to remove catalyst particles. In the photocatalytic cycle tests, the photocatalysts were centrifuged and washed with CH₃CN for the next tests.

Electrochemical measurement

Electrochemical tests were made in 0.5 M Na₂SO₄ solution as the electrolyte through the standard three-electrode system: indium–tin oxide (ITO) glass modified with catalyst samples, carbon rod, and saturated Ag/AgCl used as the working electrode, counter electrode, and the reference electrode, respectively. The working electrodes for photocurrent and Mott-Schottky spots were prepared as follows: 2 mg photocatalyst were dispersed in a mixed solution of 950 μL ethanol and 50 μL Nafion D-520 dispersion solutions to generate a homogeneous slurry. Then, 200 μL the slurry was transferred and coated on ITO glass plates (1 cm × 2 cm) and dried at room temperature.

Femtosecond transient absorption spectroscopy (TAS)measurement

The fs‐TAS measurements were conducted on a pump‐probe system (Helios, Ultrafast Systems LLC) with a maximum time delay of ~8 ns controlled by a motorized optical delay line. An 800‐nm ultrashort laser pulse was generated by an amplified Ti:sapphire laser system (Coherent Legend, 800 nm, 85 fs, 7 mJ/pulse, and 1 kHz repetition rate) and was split into two beams. The main beam was frequency‐doubled through a beta‐barium borate (BBO) crystal to 400 nm and acted as the pump pulse, and neutral‐density filters were utilized to control the power at ~160 μW. The other beam was transformed into a white‐light continuum (420–800 nm) via a sapphire to become the probe pulse, which probed the states of the specimen after photoexcitation by the pump pulse³⁸.

Calculation methods

All of the geometry optimizations were performed at the level of density functional theory (DFT) using Gaussian 09 program³⁹ at the (U)B3LYP⁴⁰/[6-31 G(d)⁴¹/SDD⁴²(Ce)] level. The absorption spectra and excited state species were obtained by using time-dependent DFT (TDDFT) and unrestricted open-shell DFT at the same level. The orbital overlap integral was calculated by the Amsterdam Density Functional (ADF 2023.101)⁴³ program package. The zero-order regular approximation (ZORA) was adopted to account for the scalar relativistic effects⁴⁴. The basis sets for describing all electrons of each atom are triple-ζ plus polarization Slater-type orbitals⁴⁵.

Data availability

Crystallographic data reported in this paper is provided in the Supplementary Information and archived at the Cambridge Crystallographic Data Center under reference number CCDC 2267826–2267828 (CeBTTD-B, CeBTTD-N, and CeBTTD-A). These data can be obtained free of charge from The Cambridge Crystallographic Data Center via “www.ccdc.cam.ac.uk/data_request/cif”. All the data supporting the findings of this study are available within the article and its Supplementary Information. Source data are provided in this paper.

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Acknowledgements

This work was financially supported by the National Key R&D Program of China (2023YFA1507204 to Y.-Q.L.), the National Natural Science Foundation of China (22225109 to Y.-Q.L., No. 22201082 to L.Z., 22301086 to X.-X.L., 22301084 to R.-H.L.), the GuangDong Basic and Applied Basic Research Foundation (No. 2021A1515110429 to L.Z.), and project funded by China Postdoctoral Science Foundation (No. 2022M721216 to L.Z., 2023T160235 to L.Z.).

Author information

These authors contributed equally: Lei Zhang, Run-Han Li.

Authors and Affiliations

School of Chemistry, South China Normal University, Guangzhou, 510006, P. R. China
Lei Zhang, Run-Han Li, **ao-**n Li, Jiang Liu, **ao-Xuan Hong, Long-Zhang Dong, Shun-Li Li & Ya-Qian Lan
College of Science, Huazhong Agricultural University, Wuhan, 430070, P. R. China
Shengyao Wang

Authors

Lei Zhang
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Run-Han Li
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**ao-**n Li
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Shengyao Wang
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Jiang Liu
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**ao-Xuan Hong
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Long-Zhang Dong
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Shun-Li Li
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Ya-Qian Lan
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Contributions

Y.-Q.L. conceived the idea and designed the experiments. X.-X.L. and L.Z. synthesized the materials and carried out the photocatalytic experiments. R.-H.L. carried out the DFT simulation for the photocatalytic reaction mechanism. L.Z., X.-X.L., S.W., J.L., X.-X.H., L.-Z.D. and S.-L.L. analyzed the data. L.Z., X.-X.L., R.-H.L. and Y.-Q.L. interpreted the results and wrote the paper.

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Correspondence to **ao-**n Li or Ya-Qian Lan.

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Zhang, L., Li, RH., Li, XX. et al. Photocatalytic aerobic oxidation of C(sp³)-H bonds. Nat Commun 15, 537 (2024). https://doi.org/10.1038/s41467-024-44833-y

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Received: 08 August 2023
Accepted: 05 January 2024
Published: 15 January 2024
DOI: https://doi.org/10.1038/s41467-024-44833-y
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Metal-organic frameworks for photocatalysis

Collection 20 May 2024

Photocatalytic aerobic oxidation of C(sp3)-H bonds

Abstract

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Introduction

Methods

Synthesis

Preparation of H4BTTD

Preparation of Ce6

Preparation of CeBTTD-B

Preparation of CeBTTD-N

Preparation of CeBTTD-A

Single-crystal X-ray diffraction

Analytical techniques

Photocatalysis activity measurement

Electrochemical measurement

Femtosecond transient absorption spectroscopy (TAS)measurement

Calculation methods

Data availability

References

Acknowledgements

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Photocatalytic aerobic oxidation of C(sp³)-H bonds

Preparation of H₄BTTD

Preparation of Ce₆