Citation: Yang WANG, Xiaoqin ZHENG, Yang LIU, Kai ZHANG, Jiahui KOU, Linbing SUN. Mn single-atom catalysts based on confined space: Fabrication and the electrocatalytic oxygen evolution reaction performance[J]. Chinese Journal of Inorganic Chemistry, ;2024, 40(11): 2175-2185. doi: 10.11862/CJIC.20240165 shu

Mn single-atom catalysts based on confined space: Fabrication and the electrocatalytic oxygen evolution reaction performance

Yang WANG ¹ ,
Xiaoqin ZHENG ¹ ,
Yang LIU ¹ ,
Kai ZHANG ¹ ,
Jiahui KOU ^2,, ,
Linbing SUN ^1,,

1.
College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing 211816, China
2.
College of Materials Science and Engineering, Nanjing Tech University, Nanjing 211816, China

Corresponding author: Jiahui KOU, jhkou@njtech.edu.cn Linbing SUN, lbsun@njtech.edu.cn
Received Date: 11 May 2024
Revised Date: 30 September 2024

Figures(13)

A simple strategy was adopted to prepare single-atom catalysts (SACs) using mesoporous silica KIT- 6 (TOK) without templating agent removal as a carrier and utilizing the confined space between the templating agent and the silica wall. After the Mn-containing precursor was introduced into the confined space of TOK by solid-phase milling, Mn SACs can be rapidly generated during the calcination. Density functional theory calculations and experimental data indicate that the Mn atoms are anchored by Si—OH groups on the carriers and exist as Mn—O—Si. The obtained Mn SACs were applied to the electrocatalytic oxygen evolution reaction, and the experimental results show that the Mn SACs exhibit better catalytic performance than the comparison samples synthesized in a carrier without confined space.
- single-atom catalyst,
- confined space,
- mesoporous silica,
- oxygen evolution reaction
1. [1]
  Cheng N C, Stambula S, Wang D, Banis M N, Liu J, Riese A, Xiao B W, Li R Y, Sham T K, Liu L M, Botton G A, Sun X L. Platinum single-atom and cluster catalysis of the hydrogen evolution reaction[J]. Nat. Commun., 2016,7(1):13638-13647. doi: 10.1038/ncomms13638
2. [2]
  Di J, Chen C, Yang S Z, Chen S M, Duan M L, Xiong J, Zhu C, Long R, Hao W, Chi Z, Chen H L, Weng Y X, Xia J X, Song L, Li S Z, Li H M, Liu Z. Isolated single atom cobalt in Bi₃O₄Br atomic layers to trigger efficient CO₂ photoreduction[J]. Nat. Commun., 2019,10:2840-2847. doi: 10.1038/s41467-019-10392-w
3. [3]
  Han G K, Zhang X, Liu W, Zhang Q H, Wang Z Q, Cheng J, Yao T, Gu L, Du C Y, Gao Y Z, Yin G P. Substrate strain tunes operando geometric distortion and oxygen reduction activity of CuN₂C₂ single-atom sites[J]. Nat. Commun., 2021,12(1):6335-6344. doi: 10.1038/s41467-021-26747-1
4. [4]
  Lee B H, Park S, Kim M, Sinha A K, Lee S C, Jung E, Chang W J, Lee K S, Kim J H, Cho S P, Kim H, Nam K T, Hyeon T. Reversible and cooperative photoactivation of single-atom Cu/TiO₂ photocatalysts[J]. Nat. Mater., 2019,18(6):620-626. doi: 10.1038/s41563-019-0344-1
5. [5]
  Wei S J, Li A, Liu J C, Li Z, Chen W X, Gong Y, Zhang Q H, Cheong W C, Wang Y, Zheng L R, Xiao H, Chen C, Wang D S, Peng Q, Gu L, Han X D, Li J, Li Y D. Direct observation of noble metal nanoparticles transforming to thermally stable single atoms[J]. Nat. Nanotechnol., 2018,13(9):856-861. doi: 10.1038/s41565-018-0197-9
6. [6]
  Tang J, Robichaux M A, Wu K L, Pei J Q, Nguyen N T, Zhou Y B, Wensel T G, Xiao H. Single-atom fluorescence switch: A general approach toward visible-light-activated dyes for biological imaging[J]. J. Am. Chem. Soc., 2019,141(37):14699-14706. doi: 10.1021/jacs.9b06237
7. [7]
  Jiao L, Zhang R, Wan G, Yang W J, Wan X, Zhou H, Shui J L, Yu S H, Jiang H L. Nanocasting SiO₂ into metal‑organic frameworks imparts dual protection to high-loading Fe single-atom electrocatalysts[J]. Nat. Commun., 2020,11(1):2831-2838. doi: 10.1038/s41467-020-16715-6
8. [8]
  He X H, Deng Y C, Zhang Y, He Q, Xiao D Q, Peng M, Zhao Y, Zhang H, Luo R C, Gan T, Ji H B, Ma D. Mechanochemical kilogram-scale synthesis of noble metal single-atom catalysts[J]. Cell Rep. Phys. Sci., 2020,1(1):100004-100016. doi: 10.1016/j.xcrp.2019.100004
9. [9]
  Sui J F, Liu H, Hu S J, Sun K, Wan G, Zhou H, Zheng X, Jiang H L. A general strategy to immobilize single-atom catalysts in metal-organic frameworks for enhanced photocatalysis[J]. Adv. Mater., 2021,34(6)2109203.
10. [10]
  Zhou H, Zhao Y F, Gan J, Xu J, Wang Y, Lv H W, Fang S, Wang Z Y, Deng Z L, Wang X Q, Liu P G, Guo W X, Mao B Y, Wang H, Yao T, Hong X, Wei S Q, Duan X Z, Luo J, Wu Y. Cation-exchange induced precise regulation of single copper site triggers room‑ temperature oxidation of benzene[J]. J. Am. Chem. Soc., 2020,142(29):12643-12650. doi: 10.1021/jacs.0c03415
11. [11]
  Liu Y W, Wu X, Li Z, Zhang J, Liu S X, Liu S J, Gu L, Zheng L R, Li J, Wang D S, Li Y D. Fabricating polyoxometalates-stabilized single-atom site catalysts in confined space with enhanced activity for alkynes diboration[J]. Nat. Commun., 2021,12(1):4205-4214. doi: 10.1038/s41467-021-24513-x
12. [12]
  Zheng X Q, Zhang K, Wang Y, Liu Y, Peng S S, Shao X B, Kou J, Sun L B. Construction of nickel single atoms by using the inherent confined space in template-occupied mesoporous silica[J]. Inorg. Chem., 2024,63(18):8312-8319. doi: 10.1021/acs.inorgchem.4c00626
13. [13]
  Gu M X, Zheng X Q, Peng S S, Qi S C, Liu X Q, Sun L B. Fabrication of Fe single atoms by utilizing the inherent confined space for phenol hydroxylation[J]. ACS Sustain. Chem. Eng., 2023,11(20):7844-7850. doi: 10.1021/acssuschemeng.3c00856
14. [14]
  Song W Q, Xiao C X, Ding J, Huang Z C, Yang X Y, Zhang T, Mitlin D, Hu W B. Review of carbon support coordination environments for single metal atom electrocatalysts (SACs)[J]. Adv. Mater., 2023,36(1):2301477-2301531.
15. [15]
  Jeong H, Shin S, Lee H. Heterogeneous atomic catalysts overcoming the limitations of single-atom catalysts[J]. ACS Nano, 2020,14(11):14355-14374. doi: 10.1021/acsnano.0c06610
16. [16]
  Sarma B B, Plessow P N, Agostini G, Concepción P, Pfänder N, Kang L, Wang F R, Studt F, Prieto G. Metal-specific reactivity in single-atom catalysts: CO oxidation on 4d and 5d transition metals atomically dispersed on MgO[J]. J. Am. Chem. Soc., 2020,142(35):14890-14902. doi: 10.1021/jacs.0c03627
17. [17]
  Zhu Z J, Yin H J, Wang Y, Chuang C H, Xing L, Dong M Y, Lu Y R, Casillas Garcia G, Zheng Y L, Chen S, Dou Y H, Liu P, Cheng Q L, Zhao H J. Coexisting single-atomic Fe and Ni sites on hierarchically ordered porous carbon as a highly efficient ORR electrocatalyst[J]. Adv. Mater., 2020,32(42)2004670. doi: 10.1002/adma.202004670
18. [18]
  Cao L L, Luo Q Q, Liu W, Lin Y K, Liu X K, Cao Y J, Zhang W, Wu Y, Yang J L, Yao T, Wei S Q. Identification of single-atom active sites in carbon-based cobalt catalysts during electrocatalytic hydrogen evolution[J]. Nat. Catal., 2018,2(2):134-141. doi: 10.1038/s41929-018-0203-5
19. [19]
  Yang Y, Zhang W Y, Tan X H, Jiang K R, Zhai S L, Li Z. Atomic-level reactive sites for electrocatalytic nitrogen reduction to ammonia under ambient conditions[J]. Coord. Chem. Rev., 2023,489:215196-215218. doi: 10.1016/j.ccr.2023.215196
20. [20]
  Wang M K, Hu Y, Pu J M, Zi Y, Huang W C. Emerging Xene-based single-atom catalysts: Theory, synthesis and catalytic applications[J]. Adv. Mater., 2023,36(3):2303492-2303599.
21. [21]
  Zheng Y, Qiao S Z. Metal-organic framework assisted synthesis of single-atom catalysts for energy applications[J]. Natl. Sci. Rev., 2018,5(5):626-627. doi: 10.1093/nsr/nwy010
22. [22]
  Gu M X, Gao L P, Peng S S, Qi S C, Shao X B, Liu X Q, Sun L B. Transition metal single atoms constructed by using inherent confined space[J]. ACS Nano, 2023,17(5):5025-5032. doi: 10.1021/acsnano.2c12817
23. [23]
  Liu Y W, Li Z, Yu Q Y, Chen Y F, Chai Z W, Zhao G F, Liu S J, Cheong W C, Pan Y, Zhang Q H, Gu L, Zheng L R, Wang Y, Lu Y, Wang D S, Chen C, Peng Q, Liu Y Q, Liu L M, Chen J S, Li Y D. A general strategy for fabricating isolated single metal atomic site catalysts in Y zeolite[J]. J. Am. Chem. Soc., 2019,141(23):9305-9311. doi: 10.1021/jacs.9b02936
24. [24]
  Jiao L, Jiang H L. Metal-organic-framework-based single-atom catalysts for energy applications[J]. Chem, 2019,5(4):786-804. doi: 10.1016/j.chempr.2018.12.011
25. [25]
  Hülsey M J, Zhang B, Ma Z R, Asakura H, Do D A, Chen W, Tanaka T, Zhang P, Wu Z L, Yan N. In situ spectroscopy-guided engineering of rhodium single-atom catalysts for CO oxidation[J]. Nat. Commun., 2019,10(1):1330-1340. doi: 10.1038/s41467-019-09188-9
26. [26]
  Qiao B T, Liang J X, Wang A Q, Xu C Q, Li J, Zhang T, Liu J Y. Ultrastable single-atom gold catalysts with strong covalent metal- support interaction (CMSI)[J]. Nano Res., 2015,8(9):2913-2924. doi: 10.1007/s12274-015-0796-9
27. [27]
  Zhao S, Chen F, Duan S B, Shao B, Li T B, Tang H L, Lin Q Q, Zhang J Y, Li L, Huang J H, Bion N, Liu W, Sun H, Wang A Q, Haruta M, Qiao B T, Li J, Liu J Y, Zhang T. Remarkable active-site dependent H₂O promoting effect in CO oxidation[J]. Nat. Commun., 2019,10(1):3824-3834. doi: 10.1038/s41467-019-11871-w
28. [28]
  Ge X, Su G R, Che W, Yang J, Zhou X, Wang Z Y, Qu Y T, Yao T, Liu W, Wu Y. Atomic filtration by graphene oxide membranes to access atomically dispersed single atom catalysts[J]. ACS Catal., 2020,10(18):10468-10475. doi: 10.1021/acscatal.0c02203
29. [29]
  Yang Z K, Chen B X, Chen W X, Qu Y T, Zhou F Y, Zhao C M, Xu Q, Zhang Q H, Duan X Z, Wu Y. Directly transforming copper􀃬 oxide bulk into isolated single-atom copper sites catalyst through gas-transport approach[J]. Nat. Commun., 2019,10(1):3734-3741. doi: 10.1038/s41467-019-11796-4
30. [30]
  Yang Z K, Zhao C M, Qu Y T, Zhou H, Zhou F Y, Wang J, Wu Y, Li Y D. Trifunctional self-supporting cobalt-embedded carbon nanotube films for ORR, OER, and HER triggered by solid diffusion from bulk metal[J]. Adv. Mater., 2019,31(12)1808043. doi: 10.1002/adma.201808043
31. [31]
  Zhang J Q, Zhao Y F, Guo X, Chen C, Dong C L, Liu R S, Han C P, Li Y D, Gogotsi Y, Wang G X. Single platinum atoms immobilized on an MXene as an efficient catalyst for the hydrogen evolution reaction[J]. Nat. Catal., 2018,1(12):985-992. doi: 10.1038/s41929-018-0195-1
32. [32]
  Zhang L H, Han L L, Liu H X, Liu X J, Luo J. Potential-cycling synthesis of single platinum atoms for efficient hydrogen evolution in neutral media[J]. Angew. Chem. Int. Ed., 2017,56(44):13694-13698. doi: 10.1002/anie.201706921
33. [33]
  Zhang L Z, Fischer J M T A, Jia Y, Yan X C, Xu W C, Wang X C, Chen J, Yang D J, Liu H W, Zhuang L Z, Hankel M, Searles D J, Huang K K, Feng S H, Brown C L, Yao X D. Coordination of atomic Co-Pt coupling species at carbon defects as active sites for oxygen reduction reaction[J]. J. Am. Chem. Soc., 2018,140(34):10757-10763. doi: 10.1021/jacs.8b04647
34. [34]
  Xiang J Q, Zhao H Y, Chen K, Yang X, Chu K. Electrocatalytic nitrite reduction to ammonia on an Rh single‑atom catalyst[J]. J. Colloid Interface Sci., 2024,659:432-438. doi: 10.1016/j.jcis.2024.01.013
35. [35]
  Liu M H, Zhang J, Su H, Jiang Y L, Zhou W L, Yang C Y, Bo S W, Pan J, Liu Q H. In situ modulating coordination fields of single-atom cobalt catalyst for enhanced oxygen reduction reaction[J]. Nat. Commun., 2024,15(1):1675-1685. doi: 10.1038/s41467-024-45990-w
36. [36]
  Pirez C, Caderon J M, Dacquin J P, Lee A F, Wilson K. Tunable KIT-6 mesoporous sulfonic acid catalysts for fatty acid esterification[J]. ACS Catal., 2012,2(8):1607-1614. doi: 10.1021/cs300161a
1. [1]
  Xin Han , Zhihao Cheng , Jinfeng Zhang , Jie Liu , Cheng Zhong , Wenbin Hu . Design of Amorphous High-Entropy FeCoCrMnBS (Oxy) Hydroxides for Boosting Oxygen Evolution Reaction. Acta Physico-Chimica Sinica, 2025, 41(4): 100033-. doi: 10.3866/PKU.WHXB202404023
2. [2]
  Endong YANG , Haoze TIAN , Ke ZHANG , Yongbing LOU . Efficient oxygen evolution reaction of CuCo₂O₄/NiFe-layered bimetallic hydroxide core-shell nanoflower sphere arrays. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 930-940. doi: 10.11862/CJIC.20230369
3. [3]
  Chuanming GUO , Kaiyang ZHANG , Yun WU , Rui YAO , Qiang ZHAO , Jinping LI , Guang LIU . Performance of MnO₂-0.39IrO_x composite oxides for water oxidation reaction in acidic media. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1135-1142. doi: 10.11862/CJIC.20230459
4. [4]
  Qiangqiang SUN , Pengcheng ZHAO , Ruoyu WU , Baoyue CAO . Multistage microporous bifunctional catalyst constructed by P-doped nickel-based sulfide ultra-thin nanosheets for energy-efficient hydrogen production from water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1151-1161. doi: 10.11862/CJIC.20230454
5. [5]
  Zhiquan Zhang , Baker Rhimi , Zheyang Liu , Min Zhou , Guowei Deng , Wei Wei , Liang Mao , Huaming Li , Zhifeng Jiang . Insights into the Development of Copper-based Photocatalysts for CO₂ Conversion. Acta Physico-Chimica Sinica, 2024, 40(12): 2406029-. doi: 10.3866/PKU.WHXB202406029
6. [6]
  Yuchen Zhou , Huanmin Liu , Hongxing Li , Xinyu Song , Yonghua Tang , Peng Zhou . 设计热力学稳定的贵金属单原子光催化剂用于乙醇的高效非氧化转化形成高纯氢和增值产物乙醛. Acta Physico-Chimica Sinica, 2025, 41(6): 100067-. doi: 10.1016/j.actphy.2025.100067
7. [7]
  Bing WEI , Jianfan ZHANG , Zhe CHEN . Research progress in fine tuning of bimetallic nanocatalysts for electrocatalytic carbon dioxide reduction. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 425-439. doi: 10.11862/CJIC.20240201
8. [8]
  Bing LIU , Huang ZHANG , Hongliang HAN , Changwen HU , Yinglei ZHANG . Visible light degradation of methylene blue from water by triangle Au@TiO₂ mesoporous catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 941-952. doi: 10.11862/CJIC.20230398
9. [9]
  Lina Guo , Ruizhe Li , Chuang Sun , Xiaoli Luo , Yiqiu Shi , Hong Yuan , Shuxin Ouyang , Tierui Zhang . 层状双金属氢氧化物的层间阴离子对衍生的Ni-Al₂O₃催化剂光热催化CO₂甲烷化反应的影响. Acta Physico-Chimica Sinica, 2025, 41(1): 2309002-. doi: 10.3866/PKU.WHXB202309002
10. [10]
  Yifan LIU , Zhan ZHANG , Rongmei ZHU , Ziming QIU , Huan PANG . A three-dimensional flower-like Cu-based composite and its low-temperature calcination derivatives for efficient oxygen evolution reaction. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 979-990. doi: 10.11862/CJIC.20240008
11. [11]
  Tian TIAN , Meng ZHOU , Jiale WEI , Yize LIU , Yifan MO , Yuhan YE , Wenzhi JIA , Bin HE . Ru-doped Co₃O₄/reduced graphene oxide: Preparation and electrocatalytic oxygen evolution property. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 385-394. doi: 10.11862/CJIC.20240298
12. [12]
  Juntao Yan , Liang Wei . 2D S-Scheme Heterojunction Photocatalyst. Acta Physico-Chimica Sinica, 2024, 40(10): 2312024-. doi: 10.3866/PKU.WHXB202312024
13. [13]
  Pengzi Wang , Wenjing Xiao , Jiarong Chen . Copper-Catalyzed C―O Bond Formation by Kharasch-Sosnovsky-Type Reaction. University Chemistry, 2025, 40(4): 239-244. doi: 10.12461/PKU.DXHX202406090
14. [14]
  Zhanggui DUAN , Yi PEI , Shanshan ZHENG , Zhaoyang WANG , Yongguang WANG , Junjie WANG , Yang HU , Chunxin LÜ , Wei ZHONG . Preparation of UiO-66-NH₂ supported copper catalyst and its catalytic activity on alcohol oxidation. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 496-506. doi: 10.11862/CJIC.20230317
15. [15]
  Xi YANG , Chunxiang CHANG , Yingpeng XIE , Yang LI , Yuhui CHEN , Borao WANG , Ludong YI , Zhonghao HAN . Co-catalyst Ni₃N supported Al-doped SrTiO₃: Synthesis and application to hydrogen evolution from photocatalytic water splitting. Chinese Journal of Inorganic Chemistry, 2025, 41(3): 440-452. doi: 10.11862/CJIC.20240371
16. [16]
  Hailang JIA , Hongcheng LI , Pengcheng JI , Yang TENG , Mingyun GUAN . Preparation and performance of N-doped carbon nanotubes composite Co₃O₄ as oxygen reduction reaction electrocatalysts. Chinese Journal of Inorganic Chemistry, 2024, 40(4): 693-700. doi: 10.11862/CJIC.20230402
17. [17]
  Qingqing SHEN , Xiangbowen DU , Kaicheng QIAN , Zhikang JIN , Zheng FANG , Tong WEI , Renhong LI . Self-supporting Cu/α-FeOOH/foam nickel composite catalyst for efficient hydrogen production by coupling methanol oxidation and water electrolysis. Chinese Journal of Inorganic Chemistry, 2024, 40(10): 1953-1964. doi: 10.11862/CJIC.20240028
18. [18]
  Peng YUE , Liyao SHI , Jinglei CUI , Huirong ZHANG , Yanxia GUO . Effects of Ce and Mn promoters on the selective oxidation of ammonia over V₂O₅/TiO₂ catalyst. Chinese Journal of Inorganic Chemistry, 2025, 41(2): 293-307. doi: 10.11862/CJIC.20240210
19. [19]
  Xiaoning TANG , Shu XIA , Jie LEI , Xingfu YANG , Qiuyang LUO , Junnan LIU , An XUE . Fluorine-doped MnO₂ with oxygen vacancy for stabilizing Zn-ion batteries. Chinese Journal of Inorganic Chemistry, 2024, 40(9): 1671-1678. doi: 10.11862/CJIC.20240149
20. [20]
  Wei Zhong , Dan Zheng , Yuanxin Ou , Aiyun Meng , Yaorong Su . K原子掺杂高度面间结晶的g-C₃N₄光催化剂及其高效H₂O₂光合成. Acta Physico-Chimica Sinica, 2024, 40(11): 2406005-. doi: 10.3866/PKU.WHXB202406005

Get Citation

PDF

XML

Metrics

PDF Downloads(7)
Abstract views(485)
HTML views(159)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142