Highly efficient photo-thermal synergistic catalysis of CO_(2)methanation over La_(1-x)Ce_(x)NiO_(3)perovskite-catalyst  

作　　者：Ting Li Zhen-Yu Zhang De-Cun Luo Bo-Yu Xu Rong-Jiang Zhang Ji-Long Yao Dan Li Tao Xie 

机构地区：[1]Institute of Industrial Catalysis,School of Chemical Engineering and Technology,Xi’an Jiaotong University,Xi’an 710049,China

出　　处：《Nano Research》2024年第9期7945-7956,共12页纳米研究（英文版）

基　　金：supported by the National Natural Science Foundation of China(No.52076176);Fundamental Research Funds for the Central Universities(Nos.xzd012023037 and xzy022023034);Innovation Capability Support Program of Shaanxi(No.2023-CX-TD-26).

摘　　要：Solar-driven photo-thermal catalytic CO_(2)methanation reaction is a promising technology to alleviate the problems posed by greenhouse gases emissions.However,designing advanced photo-thermal catalysts remains a research challenge for CO_(2)methanation reaction.In this work,a series of ABO3(A=lanthanide,B=transition metal)perovskite catalysts with Ce-substituted LaNiO3(La_(1-x)Ce_(x)NiO_(3),x=0,0.2,0.5,0.8,1)were synthesized for CO_(2)methanation.The La_(0.2)Ce_(0.8)NiO_(3) exhibited the highest CH_(4) formation rate of 258.9 mmol·g^(-1)·hcat-1,CO_(2)conversion of 55.4%and 97.2%CH_(4) selectivity at 300℃with the light intensity of 2.9 W·cm^(-2).Then the catalysts were thoroughly analyzed by physicochemical structure and optical properties characterizations.The partial substitution of the A-site provided more active sites for the adsorption and activation of CO_(2)/H_(2).The sources of the active sites were considered to be the oxygen vacancies(O_(v))created by lattice distortions due to different species of ions(La^(3+),Ce^(4+),Ce^(3+))and exsolved Ni0 by H_(2)reduction.The catalysts have excellent light absorption absorbance and low electron-hole(e^(-)/h^(+))recombination rate,which greatly contribute to the excellent performance in photo-thermal synergistic catalysis(PTC)CO_(2)methanation.The results of in situ irradiated electron paramagnetic resonance spectrometer(ISI-EPR)and ISI-X-ray photoelectron spectroscopy(XPS)indicated that the aggregation of unpaired electrons near the defects and Ni metal(from La and Ce ions to Ov and Ni0)accelerated adsorption and activation of CO_(2)/H_(2).At last,the catalyst properties and structure were correlated with the proposed reaction mechanism from the in situ diffuse reflection infrared Fourier transform spectrum(DRIFTS)measurements.The in situ precipitation of the B-site enhanced the dispersion of Ni,while its enriched photoelectrons upon illumination further promote hydrogen dissociation.More H^(*)spillover accelerated the rate-determining step(RDS)of HCOO*hydrog

关 键 词：photo-thermal catalysis CO_(2)methanation PEROVSKITE A-site substitution in situ diffuse reflection infrared Fourier transform spectrum(DRIFTS) 

分 类 号：O64[理学—物理化学]