Superior electro-catalytic performance achieved by the negatively charged boron atom on BC3/TM/graphene sandwich heterostructures

doi:10.1016/j.jmst.2024.03.078

Abstract

Abstract: The sandwich heterostructures (SHSs) are novel two-dimensional materials that hold great potential as efficient electro-catalysts. In this work, we computationally designed the BC₃/TM/Gr SHSs by intercalating transition metal atoms into the BC₃/graphene heterostructure. After the computational screening, only BC₃/Sc/Gr, BC₃/Ti/Gr, BC₃/Y/Gr and BC₃/Zr/Gr are validated as stable SHSs. The electron donation from the intercalated TM atom results in the formation of the negatively charged boron atom (B^δ^-) and activation of the BC₃ surface, making the BC₃/TM/Gr SHSs highly promising as single-atom catalysts (SACs). The BC₃/Sc/Gr and BC₃/Y/Gr SHSs exhibit potential in carbon dioxide reduction reaction (CO₂RR) and carbon monoxide reduction reaction (CORR) electro-catalysis. Particularly, when BC₃/Y/Gr SHS serves as CORR electro-catalyst, the step (*CHO→*CHOH) is a potential determining step, with an extremely low limiting potential (U_L = -0.10 V). The BC₃/Ti/Gr and BC₃/Zr/Gr SHSs are suitable as hydrogen evolution reaction (HER) electro-catalysts. Specially, the BC₃/Ti/Gr SHS serves as an ideal HER electro-catalyst in acid condition, with close-to-zero adsorption free energy (ΔG_H = 0.006 eV) and fairly low overall activation barrier (0.20 eV). By analyzing the electronic properties, the unique adsorption activity of the B^δ^- on H atom and unsaturated CO₂RR intermediates is elucidated as the origin of excellent catalytic activity of BC₃/TM/Gr SHSs, which is modulated by the intercalated TM atom. Our work is instructive to rational design of SACs towards energy conversion based on non-metal elements.

Key words: Single-atom catalysts, Heterostructure, Transition metal intercalation, DFT calculation, CO₂ reduction, Hydrogen evolution reaction

Juan Xie, Jiawen Wang, Yunpeng Shu, Juan Yang, Youyong Li, Huilong Dong. Superior electro-catalytic performance achieved by the negatively charged boron atom on BC₃/TM/graphene sandwich heterostructures[J]. J. Mater. Sci. Technol., 2025, 207: 255-265.

References

[1] S. Mallapaty, Nature 586 (2020) 482-483.
[2] D. Wei, X. Shi, H. Junge, C. Du, M. Beller, Nat. Commun. 14(2023) 3726.
[3] S.C. Peter, ACS Energy Lett. 3(2018) 1557-1561.
[4] J. Qu, X. Cao, L. Gao, J. Li, L. Li, Y. Xie, Y. Zhao, J. Zhang, M. Wu, H. Liu, Nano-Micro Lett. 15(2023) 178.
[5] P. Quaino, F. Juarez, E. Santos, W. Schmickler, Beilstein J. Nanotechnol. 5(2014) 846-854.
[6] Y. Cheng, H. Geng, X. Huang, Dalton Trans. 49(2020) 2761-2765.
[7] J. Liu, X. Yang, F. Si, B. Zhao, X. Xi, L. Wang, J. Zhang, X.-Z. Fu, J.-L. Luo, Nano Energy 103 (2022) 107753.
[8] X. Zheng, X. Han, Y. Cao, Y. Zhang, D. Nordlund, J. Wang, S. Chou, H. Liu, L. Li, C. Zhong, Y. Deng, W. Hu, Adv. Mater. 32 (2020) e2000607.
[9] J.-Y. Xue, F.-L. Li, B. Chen, H. Geng, W. Zhang, W.-Y. Xu, H. Gu, P. Braunstein, J.-P. Lang, Appl. Catal. B-Environ. 312(2022) 121434.
[10] X. Yu, J. Xie, Q. Liu, H. Dong, Y. Li, J. Colloid Interface Sci. 593(2021) 133-141.
[11] A. Mehtab, Y. Mao, S.M. Alshehri, T. Ahmad, J. Colloid Interface Sci. 652(2023) 1467-1480.
[12] L. Zhu, H. Lin, Y. Li, F. Liao, Y. Lifshitz, M. Sheng, S.T. Lee, M. Shao, Nat. Commun. 7(2016) 12272.
[13] Z.-W. Gao, J.-Y. Liu, X.-M. Chen, X.-L. Zheng, J. Mao, H. Liu, T. Ma, L. Li, W.-C. Wang, X.-W. Du, Adv. Mater. 31(2019) 1804769.
[14] J. Cai, Z. Sun, W. Cai, N. Wei, Y. Fan, Z. Liu, Q. Zhang, J. Sun, Adv. Funct. Mater. 31(2021) 2100586.
[15] C. Liu, L. Sun, L. Luo, W. Wang, H. Dong, Z. Chen, ACS Appl. Mater. Interfaces 13 (2021) 22646-22654.
[16] M.A. Ahsan, T. He, J.C. Noveron, K. Reuter, A.R.Puente-Santiago, R.Luque, Chem. Soc. Rev. 51(2022) 812-828.
[17] Y. Wan, J. Xu, R. Lv, Mater. Today 27 (2019) 69-90.
[18] R. Hou, S. Zhang, Y. Zhang, N. Li, S. Wang, B. Ding, G. Shao, P. Zhang, Adv. Funct. Mater. 32(2022) 2200302.
[19] L. Wang, Y. Li, Y. Ai, E. Fan, F. Zhang, W. Zhang, G. Shao, P. Zhang, Adv. Funct. Mater. 33(2023) 2306466.
[20] Y. Li, L. Wang, F. Zhang, W. Zhang, G. Shao, P. Zhang, Adv. Sci. 10(2023) e2205020.
[21] P. Zhang, Y. Zhao, Y. Li, N. Li, S.R.P.Silva, G. Shao, P.Zhang, Adv. Sci. 10(2023) e2206786.
[22] Y. Zhang, Z. Wu, S. Wang, N. Li, S.R.P. Silva, G. Shao, P. Zhang, InfoMat 4 (2022) e12294.
[23] Y. Zhang, P. Zhang, S. Zhang, Z. Wang, N. Li, S.R.P. Silva, G. Shao, InfoMat 3 (2021) 790-803.
[24] Q. Xia, D. Li, L. Zhao, J. Wang, Y. Long, X. Han, Z. Zhou, Y. Liu, Y. Zhang, Y. Li, A .A .A. Adam, S.Chou, Chem. Sci. 13(2022) 2841-2856.
[25] A.K. Geim, I.V. Grigorieva, Nature 499 (2013) 419-425.
[26] Y. Yan, Z. Zeng, M. Huang, P. Chen, Mater. Today Adv. 6 (2020) 100059.
[27] J. Mei, T. Liao, Z. Sun, Energy Environ. Mater. 5(2021) 115-132.
[28] F. Ling, W. Kang, H. Jing, W. Zeng, Y. Chen, X. Liu, Y. Zhang, L. Qi, L. Fang, M. Zhou, npj Comput.Mater. 5(2019) 20.
[29] R. Cheng, K. Li, H. Li, T. Zhao, Y. Wang, Q. Xue, J. Zhang, C. Fu, J. Energy Chem. 88(2024) 103-111.
[30] J.Y. Loh, F.M. Yap, W.-J. Ong, J.Mater. Sci. Technol. 179(2024) 86-97.
[31] H. Tanaka, Y. Kawamata, H. Simizu, T. Fujita, H. Yanagisawa, S. Otani, C. Oshima, Solid State Commun. 136(2005) 22-25.
[32] S.-Y. Liu, S. Liu, D.-J. Li, H. Dang, Y. Liu, S. Xue, W. Xue, S. Wang, Phys. Rev. B 88 (2013) 115434.
[33] Y. Zhang, Z.F. Wu, P.F. Gao, D.Q. Fang, E.H. Zhang, S.L. Zhang, RSC Adv. 8(2018) 1686-1692.
[34] L. Zhao, Y. Li, G. Zhou, S. Lei, J. Tan, L. Lin, J. Wang, Chin. Chem. Lett. 32(2021) 900-905.
[35] F. Zheng, H. Dong, Y. Ji, Y. Li, J. Power Sources 436 (2019) 226845.
[36] Z. Zhao, Y. Yong, R. Gao, S. Hu, Q. Zhou, X. Su, Y. Kuang, X. Li, Mater. Sci. Eng. B 271 (2021) 115266.
[37] J. Wang, Y. Yang, H. Liu, H. Dong, L. Ding, Y. Li, Chem. Phys. Lett. 792(2022) 139403.
[38] N. Zhou, Y. Qin, J. Tan, J. Cheng, S. He, H. Li, X. Wu, Mol. Phys. 120(2022) e2091050.
[39] J. Ou, X. Duan, Phys. Chem. Chem. Phys. 25(2023) 17429-17433.
[40] J. Sun, A. Chen, J. Guan, Y. Han, Y. Liu, X. Niu, M. He, L. Shi, J. Wang, X. Zhang, Energy Environ. Mater. (2023) e12693.
[41] X. Niu, X. Zhang, A. Shi, D. Sun, R. Guan, W. Shan, F. Chi, S. Li, B. Wang, X. Zhang, Appl. Phys. Lett. 122(2023) 263902.
[42] C. Zhang, Y. Jiao, T. He, S. Bottle, T. Frauenheim, A. Du, J. Phys. Chem.Lett. 9(2018) 858-862.
[43] Z. Tang, G.J. Cruz, F. Jia, Y. Wu, W. Xia, P. Zhang, Phys. Rev. Appl. 19(2023) 044085.
[44] D. Kang, Z.-W. Zuo, S.Zhang, Z. Wang, L. Zhang, Appl. Phys. Lett. 116(2020) 153103.
[45] H. Shu, Adv. Theory Simul. 4(2021) 2100275.
[46] S. Tang, Q. Dang, T. Liu, S. Zhang, Z. Zhou, X. Li, X. Wang, E. Sharman, Y. Luo, J. Jiang, J. Am. Chem.Soc. 142(2020) 19308-19315.
[47] S. Han, J. Xiong, Q. Gong, G. Liu, M. Wang, J. Liu, S. Hussain, G. Qiao, Z. Xu, Appl. Surf. Sci. 608(2023) 155204.
[48] B. Delley, J. Chem. Phys. 113(2000) 7756-7764.
[49] J.P. Perdew, K. Burke, M. Ernzerhof, Phys. Rev. Lett. 77(1996) 3865-3868.
[50] B. Delley, J. Chem. Phys. 92(1990) 508-517.
[51] S. Grimme, J. Comput. Chem. 27(2006) 1787-1799.
[52] A. Klamt, G. Schuurmann, J. Chem. Soc.-Perkin Trans. 2(1993) 799-805.
[53] M. Binetti, O. Weisse, E. Hasselbrink, A.J. Komrowski, A.C. Kummel, Faraday Discuss. 117(2000) 313-320.
[54] D. Spanjaard, M.C.Desjonquères, in: V. Bortolani, N.H. March, M.P. Tosi (Eds.), Interaction of Atoms and Molecules with Solid Surfaces, Springer US, Boston, MA, 1990, pp. 255-323.
[55] S. Guo, H. Sun, Acta Mater. 218(2021) 117212.
[56] B. Paul, N.L. Okamoto, M. Kusakari, Z. Chen, K. Kishida, H. Inui, S. Otani, Acta Mater. 211(2021) 116857.
[57] W. Yuan, Y. Ma, H. Wu, L. Cheng, J. Energy Chem. 65(2022) 254-279.
[58] G. Zhu, Y. Li, H. Zhu, H. Su, S.H. Chan, Q. Sun, ACS Catal. 6(2016) 6294-6301.
[59] H.L. Dong, Y.Y. Li, D.E. Jiang, J. Phys. Chem. C 122 (2018) 11392-11398.
[60] H.L. Dong, C. Liu, Y.Y. Li, D.E. Jiang, Nanoscale 11 (2019) 11351-11359.
[61] W. Xu, Y. Shu, M. Xu, J. Xie, Y. Li, H. Dong, Phys. Chem. Chem. Phys. 25(2023) 12872-12881.
[62] J.-H. Liu, L.-M. Yang, E. Ganz, A.C.S. Sustain, Chem. Eng. 6(2018) 15494-15502.
[63] Z.W. Chen, W. Gao, W.T. Zheng, Q. Jiang, ChemSusChem 11 (2018) 1455-1459.
[64] L. Li, B. Li, H. Guo, Y. Li, C. Sun, Z. Tian, L. Chen, Nanoscale 12 (2020) 15880-15887.
[65] L. Shi, Z. Zhou, Y. Zhang, C. Ling, Q. Li, J. Wang, Sci. Bull. 66(2021) 1186-1193.
[66] S. Mu, L. Li, R. Zhao, H. Lu, H. Dong, C. Cui, ACS Appl. Mater. Interfaces 13 (2021) 47619-47628.
[67] W. Qian, Z. Chen, J. Zhang, L. Yin, J. Mater. Sci.Technol. 99(2022) 215-222.
[68] J. Zhu, L. Hu, P. Zhao, L.Y.S.Lee, K.Y. Wong, Chem. Rev. 120(2020) 851-918.
[69] Y. Ji, H. Dong, C. Liu, Y. Li, Nanoscale 11 (2019) 454-458.
[70] Q. Tang, D.E. Jiang, ACS Catal. 6(2016) 4953-4961.
[71] H. Li, C. Deng, F. Li, M. Ma, Q. Tang, J. Mater. Inform. 3(2023) 25.
[72] Z. Zhou, npj Comput.Mater. 7(2021) 209.
[73] H. Dong, Y. Ji, L. Ding, Y. Li, Phys. Chem. Chem. Phys. 21(2019) 25535-25547.
[74] Y. Wu, C. He, W. Zhang, J. Am. Chem.Soc. 144(2022) 9344-9353.
[75] Y. Wu, C. He, W. Zhang, ACS Appl. Mater. Interfaces 13 (2021) 47520-47529 .

Superior electro-catalytic performance achieved by the negatively charged boron atom on BC₃/TM/graphene sandwich heterostructures

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

References

Related Articles 15

Recommended Articles

Metrics

Comments

[1]	Tinghui Cao, Yake Wu, Pengpeng Huang, Jiaqing Wang, Zhongyue Yang, Feng Jiang, Evan Ma. Processing heterogeneously structured oxide-dispersion-strengthened Fe-10Cr-6.1Al-0.3Zr-0.1Y alloy for simultaneously enhanced strength and ductility [J]. J. Mater. Sci. Technol., 2025, 207(0): 95-104.
[2]	S.W. Park, H.J. Lee, K.A. Nirmal, T.H. Kim, D.H. Kim, J.Y. Choi, J.S. Oh, J.M. Joo, T.G. Kim. Phase-change heterostructure with HfTe₂ confinement sublayers for enhanced thermal efficiency and low-power operation through Joule heating localization [J]. J. Mater. Sci. Technol., 2025, 204(0): 104-114.
[3]	Qi Li, Shengchao Yang, Yufan Huang, Yuwei Liang, Chunling Hu, Min Wang, Zhiyong Liu, Yanlong Tai, Jichang Liu, Yongsheng Li. Synthesis of interfacial electric field-enhanced CdS/Cd_xZn_1-_xS/ZnO ternary heterojunction by lye dissolution etching mechanism for photocatalytic H₂ production and CO₂ reduction [J]. J. Mater. Sci. Technol., 2025, 204(0): 152-165.
[4]	Kavya Kalidasan, Srinivas Mallapur, Bhavana B Kulkarni, Sanjeev P Maradur, Deepak Kumar, R Deeksha, Sakthivel Kandaiah, Prashanth Vishwa, S. Girish Kumar. Gadolinium modified g-C₃N₄ for S-Scheme heterojunction with monoclinic-WO₃: Insights from DFT studies and related charge carrier dynamics [J]. J. Mater. Sci. Technol., 2025, 204(0): 166-176.
[5]	Wei Gan, Ruixin Chen, Li Zhang, Jun Guo, Miao Zhang, Yuqing Lu, Zhaoqi Sun, Xucheng Fu. Construction of S-scheme cyano-modified g-C₃N₄/TiO₂ film with boosted charge transfer and highly hydrophilic surface for enhanced photocatalytic degradation of norfloxacin [J]. J. Mater. Sci. Technol., 2025, 206(0): 74-87.
[6]	Yuhan Liu, Jing Shang, Tong Zhu. Enhanced thermal-assisted photocatalytic CO₂ reduction by RGO/H-CN two-dimensional heterojunction [J]. J. Mater. Sci. Technol., 2024, 176(0): 36-47.
[7]	Lina Wang, Peiyi Yan, Huairui Chen, Zhuo Li, Shu Jin, Xiaoxiang Xu, Jun Qian. Augmenting reactive species over MgIn₂S₄-In₂O₃ hybrid nanofibers for efficient photocatalytic antibacterial activity [J]. J. Mater. Sci. Technol., 2024, 176(0): 83-90.
[8]	H. Wang, X.C. Luo, D.T. Zhang, C. Qiu, D.L. Chen. High-strength extruded magnesium alloys: A critical review [J]. J. Mater. Sci. Technol., 2024, 199(0): 27-52.
[9]	Linping Bao, Yushuai Jia, Xiaohui Ren, Xin Liu, Chunhui Dai, Sajjad Ali, Mohamed Bououdina, Zhanghui Lu, Chao Zeng. Cr dopants and S vacancies in ZnS to trigger efficient photocatalytic H₂ evolution and CO₂ reduction [J]. J. Mater. Sci. Technol., 2024, 199(0): 75-85.
[10]	Jinxia Yang, Zhaoxia Hu, Youlei Feng, Zehua Zou, Xiaoping Chen, Qingxiang Wang. The reconstruction of equal-mole bimetal organic framework to heterostructure for effective oxygen evolution reaction [J]. J. Mater. Sci. Technol., 2024, 203(0): 118-125.
[11]	Abbas Mohammadi, Xavier Sauvage, Fabien Cuvilly, Kaveh Edalati. Enhanced strength-ductility combination in the aluminum-gold system by heterogeneous distribution of nanoparticles via ultra-severe plastic deformation and reactive interdiffusion [J]. J. Mater. Sci. Technol., 2024, 203(0): 269-281.
[12]	T.Y. Huang, Z. Yang, S.Y. Yang, Z.H. Dai, Y.J. Liu, J.H. Liao, G.Y. Zhong, Z.J. Xie, Y.P. Fang, S.S. Zhang. Construction of 2D/2D Ti₃C₂T_x MXene/CdS heterojunction with photothermal effect for efficient photocatalytic hydrogen production [J]. J. Mater. Sci. Technol., 2024, 171(0): 1-9.
[13]	Tao Shan, Yanbo Li, Sunzai Ke, Bo Su, Lijuan Shen, Sibo Wang, Xuhui Yang, Min-Quan Yang. An embedded ReS₂@MAPbBr₃ heterostructure with downhill interfacial charge transfer for photocatalytic upgrading of biomass-derived alcohols to aldehydes and H₂ [J]. J. Mater. Sci. Technol., 2024, 179(0): 155-165.
[14]	Hongjun Dong, Lei Tong, Pingfan Zhang, Daqiang Zhu, Jizhou Jiang, Chunmei Li. Built-in electric field intensified by photothermoelectric effect drives charge separation over Z-scheme 3D/2D In₂Se₃/PCN heterojunction for high-efficiency photocatalytic CO₂ reduction [J]. J. Mater. Sci. Technol., 2024, 179(0): 251-261.
[15]	Jun Cao, Jianhong Gao, Kun Wang, Zhuoying Wu, Xinxin Zhu, Han Li, Min Ling, Chengdu Liang, Jun Chen. Constructing globally consecutive 3D conductive network using P-doped biochar cotton fiber for superior performance of silicon-based anodes [J]. J. Mater. Sci. Technol., 2024, 173(0): 181-191.