Study and application of six-component high-entropy two-dimensional materials in photothermal methanol reforming for hydrogen production
HUANG Senyan;LIU Xin;LEI Runan;DU Kai;YU Chenyang;LI Yaguang;
Abstract:
To enhance the stability and efficiency of copper-based catalysts in photothermal methanol reforming for hydrogen production,this study proposes a catalyst design strategy based on high-entropy principles. A six-component high-entropy two-dimensional Cu_2Zn_1Al_(0.5)Ce_5Zr_(0.5)In_(0.5)O_x catalyst was successfully synthesized using a polyvinylpyrrolidone(PVP)-assisted freeze-drying method.Characterization techniques, including X-ray diffraction(XRD), scanning electron microscopy(SEM), transmission electron microscopy(TEM), and nitrogen adsorption-desorption analysis, confirmed the single-phase crystal structure and nanosheet morphology of the catalyst,along with its superior anti-sintering and anti-oxidation properties. In thermal catalytic reactions,the catalyst exhibited a hydrogen production rate of 1 887.94 mmol/(g·h) at 450 °C. When integrated with a novel photothermal conversion device,the catalyst demonstrated remarkable photothermal catalytic activity under a solar intensity of 2 kW/m2,achieving a methanol steam reforming hydrogen production rate of 1 402.12 mmol/(g·h) while maintaining stability over 72 hours,indicating exceptional long-term durability.Further experiments revealed that the high performance of this catalyst is primarily attributed to the thermodynamic stability and unique porous structure derived from its high-entropy characteristics. These features significantly increased the number of catalytic active sites and enhanced resistance to high-temperature conditions. Compared to traditional catalysts,the six-component highentropy Cu_2Zn_1Al_(0.5)Ce_5Zr_(0.5)In_(0.5)O_x exhibited significantly improved catalytic performance and stability in photothermal methanol reforming for hydrogen production, addressing the sintering challenges caused by temperature fluctuations in outdoor photothermal systems. This study not only provides a novel and efficient catalyst design strategy for the photothermal catalysis field but also advances the practical application of high-entropy materials under complex reaction conditions. By integrating high-entropy materials with photothermal catalytic technology,this work offers theoretical support and practical solutions for the sustainable and efficient production of hydrogen energy,showcasing the broad industrial application potential of this catalyst in hydrogen production.
Key Words: PVP-assisted freeze-drying method;high-entropy materials;photothermal catalysis technology;methanol steam reforming for hydrogen production;catalyst
Foundation: 国家自然科学基金资助项目(52371220,U23A20139)
Authors: HUANG Senyan;LIU Xin;LEI Runan;DU Kai;YU Chenyang;LI Yaguang;
DOI: 10.13226/j.issn.1006-6772.HH24111201
References:
- [1]LIU Z,GUAN D,WEI W,et al. Reduced carbon emission estimates from fossil fuel combustion and cement production in China[J]. Nature,2015,524(7565):335-8.
- [2]BUHRE B J P, ELLIOTT L K, SHENG C D, et al. Oxy-fuel combustion technology for coal-fired power generation[J].Progress in Energy and Combustion Science, 2005, 31(4):283-307.
- [3]XU S, CHANSAI S, STERE C, et al. Sustaining metal–organic frameworks for water–gas shift catalysis by non-thermal plasma[J].Nature Catalysis,2019,2(2):142-8.
- [4]YOSHIKAWA K, KAWASAKI H, YOSHIDA W, et al. Silicon heterojunction solar cell with interdigitated back contacts for a photoconversion efficiency over 26%[J]. Nature Energy, 2017,2(5):17032.
- [5]LIN L, ZHOU W, GAO R, et al. Low-temperature hydrogen production from water and methanol using Pt/α-MoC catalysts[J].Nature,2017,544(7648):80-3.
- [6]WU X,WU S. Production of high-purity hydrogen by sorptionenhanced steam reforming process of methanol[J]. Journal of Energy Chemistry,2015,24(3):315-21.
- [7]LI Y,BAI X,YUAN D,et al. General heterostructure strategy of photothermal materials for scalable solar-heating hydrogen production without the consumption of artificial energy[J]. Nature Communications,2022,13(1):776.
- [8]KUNG H H. Deactivation of methanol synthesis catalysts-A review[J]. Catalysis Today,1992,11(4):443-53.
- [9]LABAKI M,LAMONIER J F,SIFFERT S,et al. Influence of the preparation method on the activity and stability of copper–zirconium catalysts for propene deep oxidation reaction[J]. Colloids and Surfaces A:Physicochemical and Engineering Aspects,2003,227(1):63-75.
- [10]TWIGG M V,SPENCER M S. Deactivation of copper metal catalysts for methanol decomposition,methanol steam reforming and methanol synthesis[J]. Topics in Catalysis,2003,22(3):191-203.
- [11]CHENG W-H. Deactivation and regeneration of Cu/Cr based methanol decomposition catalysts[J]. Applied Catalysis B:Environmental,1995,7(1):127-36.
- [12]MOBARAKEH M D, DARIAN J T, KARIMZADEH R, et al.Deactivation kinetics of methanol steam reforming catalyst for pure hydrogen generation[J]. Chemical Technology:An Indian Journal,2008,3.
- [13]ALBEDWAWI S H,ALJABERI A,HAIDEMENOPOULOS G N,et al. High entropy oxides-exploring a paradigm of promising catalysts:A review[J]. Materials&Design,2021,202:109534.
- [14]ROST C M, SACHET E, BORMAN T, et al. Entropy-stabilized oxides[J]. Nature Communications,2015,6(1):8485.
- [15]SUN Y,DAI S. High-entropy materials for catalysis:A new frontier[J]. Science Advances,7(20):eabg1600.
- [16]SARKAR A,WANG Q,SCHIELE A,et al. High-entropy oxides:Fundamental aspects and electrochemical properties[J]. Advanced Materials,2019,31(26):1806236.
- [17]RILEY C,DE LA RIVA A,PARK J E,et al. A high entropy oxide designed to catalyze CO oxidation without precious metals[J].ACS Applied Materials&Interfaces,2021,13(7):8120-8128.
- PVP-assisted freeze-drying method
- high-entropy materials
- photothermal catalysis technology
- methanol steam reforming for hydrogen production
- catalyst
- HUANG Senyan
- LIU Xin
- LEI Runan
- DU Kai
- YU Chenyang
- LI Yaguang
- Research Center for Solar Driven Carbon Neutrality
- Hebei University
- HUANG Senyan
- LIU Xin
- LEI Runan
- DU Kai
- YU Chenyang
- LI Yaguang
- Research Center for Solar Driven Carbon Neutrality
- Hebei University