Effect of Morphology Regulated ZnO Facets on the Photocatalytic Selective Oxidation of Methane

Qiang Ding; Haozhi Wang; Yue Zhao; Yanqun Chen; Jiancheng Wang; Zhijun Zuo

doi:10.11949/0438-1157.20260538

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Effect of Morphology Regulated ZnO Facets on the Photocatalytic Selective Oxidation of Methane

更新时间：2026-08-14

- Effect of Morphology Regulated ZnO Facets on the Photocatalytic Selective Oxidation of Methane
- CIESC Journal (2026)
- 作者机构：
  
  1.太原理工大学环境与生态学院，山西太原 030024
  2.太原理工大学化学与化工学院，山西太原 030024
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20260538
  CLC： TQ51
- Received：15 April 2026，
  
  Revised：2026-08-08，
  
  Accepted：14 August 2026，
- 稿件说明：
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Qiang Ding, Haozhi Wang, Yue Zhao, et al. Effect of Morphology Regulated ZnO Facets on the Photocatalytic Selective Oxidation of Methane[J/OL]. CIESC Journal, 2026.
DOI：

Qiang Ding, Haozhi Wang, Yue Zhao, et al. Effect of Morphology Regulated ZnO Facets on the Photocatalytic Selective Oxidation of Methane[J/OL]. CIESC Journal, 2026. DOI： 10.11949/0438-1157.20260538.

摘要

为探究ZnO催化剂晶面对光催化甲烷选择性氧化反应路径的影响机制，本研究基于形貌工程策略，通过调控催化剂表面自由基微环境，采用水热法合成了两种不同晶面暴露的ZnO材料：一种是由纳米颗粒组装而成的纳米片状结构（ZnO-NS），主要暴露(100)晶面；另一种为不规则纳米棒（ZnO-NR），主要暴露(101)晶面。实验结果表明，ZnO-NS的液相产物主要为甲醛和甲酸，而ZnO-NR的液相产物除甲醛和甲酸外还生成乙醛。以ZnO-NS为催化

剂时，甲醛产率最高可达13.12 μmol h

-1

，对应的选择性为89.38%；以ZnO-NR为催化剂时，乙醛选择性最高为35.43%，此时乙醛产率为2.74 μmol h

-1

。表征与理论计算结果表明，ZnO-NS表面高浓度的•OH可促进•CH

定向氧化为甲醛，有效抑制C-C偶联路径；而ZnO-NR表面较低的•CH

/•OH浓度比则使部分•CH

发生偶联生成乙醛。本研究从表面自由基反应动力学层面阐明了形貌工程调控甲烷转化选择性的微观机制，为高效光催化甲烷转化催化剂的设计提供了新思路。

Abstract

To investigate the influence mechanism of ZnO facets on the reaction pathway of photocatalytic selective oxidation of methane

this study employed a morphology engineering strategy to regulate the surface radical microenvironment. Two ZnO materials with different exposed crystal facets were synthesized via a hydrothermal method: one is a nanosheet-assembled structure (ZnO-NS) predominantly exposing the (100) facet

and the other is an irregular nanorod structure (ZnO-NR) predominantly exposing the (101) facet. Experimental results show that the liquid-phase products on ZnO-NS are mainly formaldehyde and formic acid

while the liquid-phase products on ZnO-NR are mainly formaldehyde

formic acid and acetaldehyde. The highest formaldehyde production rate on ZnO-NS reaches 13.12 μmol h

-1

with a corresponding selectivity of 89.38%. The highest acetaldehyde selectivity on ZnO-NR reaches 35.43%

with a corresponding production rate of 2.74 μmol h

-1

. Characterization and theoretical calculation results reveal that the relative concentrations of •OH and •CH

are the key factors governing product selectivity. The high concentration of •OH on the ZnO-NS surface promotes the oriented oxidation of •CH

to formaldehyde

effectively suppressing the C-C coupling pathway; in contrast

the lower •CH

/•OH concentration ratio on the ZnO-NR surface allows partial •CH

to undergo coupling to form acetaldehyde. This work elucidates

from the perspective of surface radical reaction kinetics

the microscopic mechanism by which morphology engineering regulates the selectivity of methane conversion

and prov

ides new insights into the rational design of efficient photocatalysts for methane conversion.

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Keywords

references

Wu Y , Gao Z H , Liu L , et al . Photocatalytic selective conversion of methane to C2 products under mild conditions [J ] . ACS Sustainable Chemistry & Engineering , 2025 , 13 ( 49 ): 20994 - 21014 .

崔梦瑶 , 康安泰 , 代卫炯 , 等 . 负载铜分子筛催化甲烷选择性氧化制甲醇性能研究 [J ] . 化工学报 , DOI: 10.11949/0438-1157.20251406 http://dx.doi.org/10.11949/0438-1157.20251406 .

Cui M Y , Kang A T , Dai W J , et al . Performance of copper‑loaded zeolite for selective oxidation of methane to methanol [J ] . CIESC Journal , 2026 , DOI: 10.11949/0438-1157.20251406 http://dx.doi.org/10.11949/0438-1157.20251406 .

Shi Y Y , Liu S Z , Liu Y M , et al . Quasicatalytic and catalytic selective oxidation of methane to methanol over solid materials: a review on the roles of water [J ] . Catalysis Reviews , 2020 , 62 ( 3 ): 313 - 345 .

杨娟 , 郝静怡 , 戴俊 , 等 . 介孔WO 3 /H 2 O 2 光催化氧化低浓度瓦斯制甲醇性能与机理 [J ] . 煤炭学报 , 2019 , 44 ( 10 ): 3107 - 3116 .

Yang J , Hao J Y , Dai J , et al . Performance and mechanism of photocatalytic oxidation of low concentration coal-mine gas into methanol in mesoporous WO 3 /H 2 O 2 system [J ] . Journal of China Coal Society , 2019 , 44 ( 10 ): 3107 - 3116 .

Wang W J , Zhang H N , Xu P , et al . Continuous selective oxidation of methane to methanol by thermal-assisted photocatalysis over NiO/ZnO [J ] . Journal of Colloid and Interface Science , 2025 , 699 : 138190 .

杨娟 , 冷冲冲 , 张鸽 , 等 . 铜改性TiO 2 /碳纤维膜光热协同催化H 2 O 2 脱除燃煤烟气中NO性能 [J ] . 煤炭学报 , 2024 , 49 ( 4 ): 2099 - 2114 .

Yang J , Leng C C , Zhang G , et al . Performance study on removal of NO in coal-fired flue gas via photothermal syner-gistic catalysis of H 2 O 2 over copper-modified TiO 2 /carbon fiber film [J ] . Journal of China Coal Society , 2024 , 49 ( 4 ): 2099 - 2114 .

符淑瑢 , 张勤生 , 鲁金芝 , 等 . ZnO基光电极的构筑及其光电催化水分解性能研究进展 [J ] . 化工进展 , 2021 , 40 ( 3 ): 1413 - 1424 .

Fu S R , Zhang Q S , Lu J Z , et al . Research progress of fabrication of ZnO-based photoanode and photoelectrocatalytic water splitting performances [J ] . Chemical Industry and Engineering Progress , 2021 , 40 ( 3 ): 1413 - 1424 .

孟庆明 , 王鉴 . 并流沉淀法合成Fe掺杂ZnO及其光催化脱氮性能 [J ] . 化工学报 , 2017 , 68 ( 1 ): 437 - 443 .

Meng Q M , Wang J . Synthesis of Fe-doped ZnO by parallel flow precipitation method and its photocatalytic denitrification performance [J ] . CIESC Journal , 2017 , 68 ( 1 ): 437 - 443 .

Chen Y Q , Mao L X , Zhang R X , et al . An efficient Au/ZnO catalyst for the photocatalytic conversion of methane to formaldehyde [J ] . Chemical Engineering Journal , 2024 , 498 : 155792 .

佟丽丽 , 陈英 , 艾敏华 , 等 . ZnO/WO 3 异质结光催化环烯烃[2+2 ] 环加成制备高能量密度燃料 [J ] . 化工学报 , 2025 , 76 ( 9 ): 4882 - 4892 .

Tong L L , Chen Y , Ai M H , et al . ZnO/WO 3 heterojunction modulated [2+2 ] photocycloaddition of cycloolefins for high-energy-density fuels production [J ] . CIESC Journal , 2025 , 76 ( 9 ): 4882 - 4892 .

李萌 . 不同形貌ZnO材料的制备及光催化性能研究 [D ] . 新乡 : 河南师范大学 , 2013 .

Li M . Study on the preparetion and photocatalytic property of ZnO with different morphologies [D ] . Xinxiang : Henan Normal University , 2013 .

于艳 , 姚秉华 , 曹宝月 , 等 . pH值对SnO 2 /ZnO形貌及光催化性能的影响 [J ] . 硅酸盐学报 , 2019 , 47 ( 6 ): 834 - 841 .

Yu Y , Yao B H , Cao B Y , et al . Effect of pH value on morphology and photocatalytic performance of SnO 2 /ZnO [J ] . Journal of the Chinese Ceramic Society , 2019 , 47 ( 6 ): 834 - 841 .

Ren L , Zhang H Y , Yan X Y , et al . Remarkable influence of morphology on hexagonal wurtzite ZnO for photothermocatalytic synergetic oxidation of benzene [J ] . Journal of Environmental Chemical Engineering , 2026 , 14 ( 2 ): 121534 .

张庆凤 . ZnO{101}半极性面负载Au催化CO氧化的实验和理论研究 [D ] . 武汉 : 中南民族大学 , 2018 .

Zhang Q F . Experimental and theoretical studies of the catalytic CO oxidation by gold supported on the semi-polar ZnO{101}surfaces [D ] . Wuhan : South-central University for Nationalities , 2018 .

Chebbi A , Sinopoli A , Abotaleb A , et al . Photocatalytic conversion of carbon dioxide, methane, and air for green fuels synthesis [J ] . Catalysis Science & Technology , 2023 , 13 ( 17 ): 4895 - 4918 .

Blöchl P E . Projector augmented-wave method [J ] . Physical Review B , 1994 , 50 ( 24 ): 17953 - 17979 .

Kresse G , Furthmüller J . Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set [J ] . Computational Materials Science , 1996 , 6 ( 1 ): 15 - 50 .

Kresse G , Hafner J . Ab initio molecular dynamics for liquid metals [J ] . Physical Review B , 1993 , 47 ( 1 ): 558 - 561 .

Perdew J P , Burke K , Ernzerhof M . Generalized gradient approximation made simple [J ] . Physical Review Letters , 1996 , 77 ( 18 ): 3865 - 3868 .

Dudarev S L , Botton G A , Savrasov S Y , et al . Electron-energy-loss spectra and the structural stability of nickel oxide: An LSDA+U study [J ] . Physical Review B , 1998 , 57 ( 3 ): 1505 - 1509 .

Cao X M , Burch R , Hardacre C , et al . An understanding of chemoselective hydrogenation on crotonaldehyde over Pt(111) in the free energy landscape: The microkinetics study based on first-principles calculations [J ] . Catalysis Today , 2011 , 165 ( 1 ): 71 - 79 .

Clay J P , Greeley J P , Ribeiro F H , et al . DFT comparison of intrinsic WGS kinetics over Pd and Pt [J ] . Journal of Catalysis , 2014 , 320 : 106 - 117 .

Chen Y Q , Zhang H N , Wang W J , et al . Water splitting promotes the proton-coupled electron transfer process for selective methane photooxidation [J ] . ACS Catalysis , 2026 : acscatal. 6 c 04438 .

郭润泽 , 吴建云 , 王文宾 , 等 . Keggin型杂多酸盐复合材料的制备及其光催化甲烷氧化的性能研究 [J ] . 中国科学: 化学 , 2025 , 55 ( 10 ): 3063 - 3072 .

Guo R Z , Wu J Y , Wang W B , et al . Fabrication of Keggin heteropolyacids composite material and their photocatalytic properties for methane oxidation [J ] . Scientia Sinica Chimica) , 2025 , 55 ( 10 ): 3063 - 3072 .

Yuniar G , Saputera W H , Sasongko D , et al . Recent advances in photocatalytic oxidation of methane to methanol [J ] . Molecules , 2022 , 27 ( 17 ): 5496 .

苏哲林 , 李敏麒 , 杨超 , 等 . Co掺杂ZnO/SiO 2 复合脱硫剂常温脱硫性能及再生性能 [J ] . 煤炭学报 , 2023 , 48 ( 10 ): 3928 - 3936 .

Su Z L , Li M Q , Yang C , et al . Desulfurization and regeneration performance of Co doped ZnO/SiO 2 composite desulfurizer at room temperature [J ] . Journal of China Coal Society , 2023 , 48 ( 10 ): 3928 - 3936 .

史晋宜 , 魏庆玲 , 徐誉宁 . 纤锌矿ZnO的形貌调控及其光催化性能研究 [J ] . 化工生产与技术 , 2025 , 31 ( 4 ): 10 - 12, 24 .

Shi J Y , Wei Q L , Xu Y N . Study on the morphological control and photocatalytic performance of ZnO from wurtzite [J ] . Chemical Production and Technology , 2025 , 31 ( 4 ): 10 - 12, 24 .

Hanh N H , Thi Minh Nguyet Q , Van Chinh T , et al . Enhanced photocatalytic efficiency of porous ZnO coral-like nanoplates for organic dye degradation [J ] . RSC Advances , 2024 , 14 ( 21 ): 14672 - 14679 .

Suganya Josephine G A , Jayaprakash K , Meenakshi G , et al . Photocatalytically active ZnO flaky nanoflowers for environmental remediation under solar light irradiation: effect of morphology on photocatalytic activity [J ] . Bulletin of Materials Science , 2021 , 44 ( 4 ): 247 .

Rodnyi P A , Khodyuk I V . Optical and luminescence properties of zinc oxide (Review) [J ] . Optics and Spectroscopy , 2011 , 111 ( 5 ): 776 - 785 .

张春梅 , 王东栋 , 方明 , 等 . 原子层沉积制备氧化锌纳米薄膜的光学性质研究 [J ] . 光谱学与光谱分析 , 2016 , 36 ( 1 ): 27 - 30 .

Zhang C M , Wang D D , Fang M , et al . Optical properties of ZnO films fabricated by atomic layer deposition [J ] . Spectroscopy and Spectral Analysis , 2016 , 36 ( 1 ): 27 - 30 .

Nosaka Y , Nosaka A Y . Generation and detection of reactive oxygen species in photocatalysis [J ] . Chemical Reviews , 2017 , 117 ( 17 ): 11302 - 11336 .

Wang P , Feng X Y , Liang J , et al . Dual-site engineering of Au/Sr-ZnO photocatalysts for lattice oxygen-activated methane coupling to ethane with high selectivity [J ] . Applied Catalysis B: Environment and Energy , 2025 , 375 : 125437 .

李子怡 , 冉晨熙 , 张跃飞 , 等 . 高效CO 2 光还原的ZnIn 2 S 4 基光催化剂设计及产物定向调控策略 [J ] ．化工学报 . DOI: 10.11949/0438-1157.20251346 http://dx.doi.org/10.11949/0438-1157.20251346

Li Z Y , Ran C X , Zhang Y F , et al . Design of ZnIn₂S₄-based photocatalysts for efficient CO 2 photoreduction and strategy for targeted regulation of products [J ] . CIESC Journal , DOI: 10.11949/0438-1157.20251346 http://dx.doi.org/10.11949/0438-1157.20251346

Wu P P , Chu Y Y , Wang M L , et al . Subnanometric MoO x clusters limit overoxidation during photocatalytic CH 4 conversion to oxygenates over TiO 2 [J ] . Nature Communications , 2025 , 16 : 4207 .

许新然 , 李晓聪 , 刘璇 , 等 . Co/Cl掺杂提升嘧啶化氮化碳光催化CO 2 还原性能及其机理研究 [J ] . 化工学报 . DOI: 10.11949/0438-1157.20251343 http://dx.doi.org/10.11949/0438-1157.20251343 .

Xu X R , Li X C , Liu X , et al . Co/Cl doping for enhancing photocatalytic CO 2 reduction performance of pyrimidine-modified carbon nitride and its mechanism [J ] . CIESC Journal , DOI: 10.11949/0438-1157.20251343 http://dx.doi.org/10.11949/0438-1157.20251343 .

Gong H T , Zhang L , Deng C H , et al . Selective photocatalytic aerobic oxidation of methane to methyl hydroperoxide by ZnO-loaded single-atomic ruthenium oxide catalyst [J ] . Journal of the American Chemical Society , 2025 , 147 ( 11 ): 9134 - 9146 .

李晓红 , 董一宴 , 寇曦皓 , 等 . 多金属氧酸盐刻蚀双金属有机框架促进光催化CO 2 还原 [J ] . 化工学报 . DOI： 10.11949/0438-1157.20251265 http://dx.doi.org/10.11949/0438-1157.20251265 .

Li X H , Dong Y Y , Kou X H , et al . Etching of bimetallic metal–organic frameworks by polyoxometalates to promote photocatalytic CO 2 reduction [J ] . CIESC Journal , DOI： 10.11949/0438-1157.20251265 http://dx.doi.org/10.11949/0438-1157.20251265 .

Sun M Y , Zhang L , Li Y , et al . Recovering Ag+ with nano-MOF-303 to form Ag/AgCl/MOF-303 photocatalyst: The role of stored Cl− ions [J ] . Chinese Chemical Letters , 2025 , 36 ( 2 ): 110035 .

Yu S X , Fan S Y , Duan J , et al . Zn-Fe pair sites catalyst for highly selective photocatalytic oxidation of methane to formaldehyde [J ] . Applied Catalysis B: Environment and Energy , 2025 , 365 : 124930 .

Zhao Y B , Luo J Y , Hu H J , et al . AuPd nanoparticle-decorated ultrathin Bi 2 TiO 4 F 2 sheets for photocatalytic methane oxidation [J ] . New Journal of Chemistry , 2022 , 46 ( 22 ): 10545 - 10549 .

Pal R , Farnood R . Spectro-kinetic modelling of photocatalytic oxidation of heterocyclic compounds in a continuous-flow packed bed reactor [J ] . RSC Advances , 2026 , 16 ( 22 ): 20282 - 20294 .

Si F Y , Lv M Y , Cai X , et al . Photocatalytic oxidation of methane to C1 oxygenates promoted by Fe–N–Ti electron bridge [J ] . Applied Catalysis B: Environment and Energy , 2024 , 358 : 124417 .

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