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Researchers Realize Photocatalytic Selective Oxidation of Methane by Bismuth Vanadate with Quantum Size

Feb 04, 2021

A research team led by Prof. TANG Zhiyong from the National Center for Nanoscience and Technology (NCNST) of the Chinese Academy of Sciences (CAS), collaborating with Profs. HAN Dongxue and FAN Yingying from Guangzhou University, realized photocatalytic selective oxidation of methane (CH4) by quantum-sized bismuth vanadate. The study was published in Nature Sustainability.

Photocatalytic CH4 oxidation can generate many types of value-added chemicals at room temperature using sustainable radiation with light instead of thermal activation. Among them methanol (CH3OH) and formaldehyde (HCHO) are two major targets because of their application as widely used chemicals or building blocks.

However, due to the complicated and energy-downhill process of CH4 oxidation: CH4 → CH3OOH → CH3OH → HCHO → CO2, there is a trade-off between catalytic productivity and selectivity to the intermediates of CH3OH and HCHO, respectively.

The researchers in this study reported a highly selective aerobic conversion of CH4 to CH3OH and HCHO using quantum-sized BiVO4 nanoparticles (q-BiVO4) as photocatalyst at room temperature.

They developed a hard-template method to prepare the q-BiVO4 nanoparticles whose size (~4.5 nm) is close to the Bohr radius (2 nm), which indicates a strong quantum confinement effect. Benefiting from the quantum size, q-BiVO4 is characteristic of high kinetic energy and large specific surface enabling effective conversion of CH4 to CH3OH and HCHO. The selectivity to CH3OH and HCHO can be tuned by altering the amount of oxygen and solvent, reaction time, irradiation wavelength and intensity. 

Since HCHO is the oxidation product of CH3OH, increasing the oxidation capacity is an efficient strategy for elevating its selectivity. Thus, ultraviolet irradiation (300-400 nm, 170 mW cm-2) was used to promote the conversion of CH4 and improve the oxidation of CH3OH to HCHO. Conversely, diminished oxidation can enhance the selectivity for CH3OH. Using visible light (400-780 nm), a remarkable CH3OH selectivity of 96.6% was achieved. 

According to the conducted isotopic tests, the capture of intermediates, and the identification of the rate-determining step, the researchers proposed a feasible radical mechanism for the oxidation of CH4 on q-BiVO4.  

Under light irradiation, q-BiVO4 is excited to produce hydroxyl radicals (HO·) for C-H bond cleavage. The generated H3C· combines with O2, a proton and one electron to form CH3OOH, which will be reduced by electrons or decomposed under UV irradiation to CH3OH. Upon oxidation, the as-formed CH3OH is further activated to produce HCHO. 

This study provides a more accurate understanding of the photocatalytic CH4 oxidation process.

CH4 contributing 70-90% to the composition of natural gas, has been recognized as an indispensable feedstock in the manufacture of fuels and chemicals. Its large-scale transformation to liquid fuels and chemicals is performed with traditional syngas and Fischer-Tropsch technology via an indirect process under high operation temperature (800oC - 900oC).
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TANG Zhiyong

National Center for Nanoscience and Technology

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Selective photocatalytic oxidation of methane by quantum-sized bismuth vanadate

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