搜索

x

留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

硼掺杂纤维红磷烯的电子结构及其高效光催化析氢性能的理论研究

卢一林 董盛杰 崔方超 陈东明 毛卓

引用本文:
Citation:

硼掺杂纤维红磷烯的电子结构及其高效光催化析氢性能的理论研究

卢一林, 董盛杰, 崔方超, 陈东明, 毛卓

Theoretical Study on the Electronic Structure and Efficient Photocatalytic Hydrogen Evolution of Boron-Doped Fibrous Red Phosphorene

Lu Yi-Lin, Dong Shengjie, Cui Fangchao, Chen Dongming, Mao Zhuo
Article Text (iFLYTEK Translation)
PDF
导出引用
  • 在能源危机与环境污染的双重挑战下,光催化分解水制氢技术因其绿色可持续特性成为清洁能源领域的研究热点.纤维红磷(FRP)作为一种新型准一维半导体材料,凭借其适中的带隙、高载流子迁移率及优异的空气稳定性,展现出显著的光催化析氢潜力.基于第一性原理计算,我们系统探究了一系列非金属元素X(B、C、N、O、Si、S、As和Se)掺杂对单层FRP电子结构及催化性能的调控机制.结果表明,杂质X能有效提升单层FRP的析氢反应(HER)活性.其中,四种掺杂体系(S掺杂位点1、B掺杂位点1/2/5)表现出优异的HER催化活性.尤其是B掺杂位点2体系,具有最理想的氢吸附自由能,其过电位与贵金属Pt催化剂相当.电子结构分析发现,HER催化活性的增强与吸附位点X pz带中心的下移密切相关,氢吸附自由能与X pz带中心呈现正相关性,表明X pz带中心可作为调控析氢反应活性的关键电子描述符.杂化泛函计算进一步证实,B掺杂体系的带边位置能够横跨水的氧化还原电势两侧,且光吸收范围覆盖可见光区域,表明了该体系在光催化全解水应用中的热力学可行性与光谱响应优势.该研究为基于非金属掺杂策略设计高效非金属基光催化材料提供了重要理论指导.
    Under the dual challenges of the energy crisis and environmental pollution, the technology of photocatalytic water splitting for hydrogen production has become a research hotspot in clean energy due to its green and sustainable characteristics. As a novel quasi-one-dimensional semiconductor material, fibrous red phosphorene (FRP) exhibits remarkable photocatalytic hydrogen evolution potential, owing to its moderate bandgap, high carrier mobility, and excellent air stability. Based on first-principles calculations, we systematically investigated the regulatory mechanisms of a series of non-metallic elements X (B, C, N, O, Si, S, As, and Se) doping on the electronic structure and catalytic performance of single-layer FRP. The results show that the element X can effectively enhance the hydrogen evolution reaction (HER) activity of single-layer FRP. Among them, four doped systems (S-doped at site 1, B-doped at sites 1/2/5) exhibit excellent catalytic activity for HER. In particular, the B-doped system at site 2 has the most ideal free energy of hydrogen adsorption (ΔGH*), and its overpotential (η = -0.074 V) is comparable to that of the noble metal Pt catalyst. Through the analysis of the electronic structure, it is found that the enhancement of the HER catalytic activity is closely related to the downward shift of the X pz-band center at the adsorption site. There is a direct proportional relationship between ΔGH* and the X pz-band center (R2 ≥ 0.78), indicating that the X pz-band center can serve as a key electronic descriptor for regulating the HER activity. Further verification by calculations using the HSE06 hybrid functional shows that the band edge positions of the B-doped system can span both sides of the redox potential of water, and the light absorption range covers the visible light region, indicating the thermodynamic feasibility and spectral response advantages of this system in the application of photocatalytic overall water splitting. This study provides important theoretical guidance for the design of efficient FRP-based photocatalytic materials based on the non-metallic doping strategy.
  • [1]

    Fujishima A, Honda K 1972Nature 238 37

    [2]

    Yin W J, Tang H, Wei S H, et al 2010Phys. Rev. B 82045106

    [3]

    Wei W, Dai Y, Guo M, Yu L, Huang B 2009J. Phys. Chem. C 113 15046

    [4]

    Qian C, Qin K, Zhaoxiong X 2021Acta Chim. Sin. 79 10(in Chinese). (陈钱, 匡勤, 谢兆雄2021化学学报79 10.)

    [5]

    Zou J, Liao G, Jiang J, Xiong Z, Bai S, Wang H, Wu P, Zhang P, Li X 2022Chin. J. Struct. Chem. 41 25

    [6]

    Zhang Z, Zhu Y, Chen X, Zhang H, Wang J 2019Adv. Mater. 31 1806626

    [7]

    Wang X, Ma M, Zhao X, Jiang P, Wang Y, Wang J, Zhang J, Zhang F 2023Small Struct. 4 2300123

    [8]

    Zhu Y, Ren J, Zhang X, Yang D 2020Nanoscale 12 13297

    [9]

    Chen Z, Zhu Y, Wang Q, Liu W, Cui Y, Tao X, Zhang D 2019Electrochim. Acta 295 230

    [10]

    Bachhuber F, Appen J, Dronskowski R, Schmidt P, Nilges T, Pfitzner A, Weihrich R 2014Angew. Chem. Int. Ed. 53 11629

    [11]

    Smith J B, Hagaman D, DiGuiseppi D, Schweitzer-Stenner R, Ji H F 2016Angew. Chem. Int. Ed. 55 11829

    [12]

    Amaral P E M, Nieman G P, Schwenk G R, Jing H, Zhang R, Cerkez E B, Strongin D, Ji H F 2019Angew. Chem. Int. Ed. 58 6766

    [13]

    Thurn H, Kerbs H 2010Angew. Chem. Int. Ed. 5 1047

    [14]

    Thurn H, Krebs H 1966Angew. Chem. Int. Ed. Engl. 5 1047

    [15]

    Tsai H-S, Lai C-C, Hsiao C-H, Medina H, Su T-Y, Ouyang H, Chen T-H, Liang J-H, Chueh Y-L 2015ACS Appl. Mater. Interfaces 7 13723

    [16]

    Shen Z, Hu Z, Wang W, Lee S F, Chan D K L, Li Y, Gu T, Yu J C 2014Nanoscale 6 14163

    [17]

    Sun Z, Chen W, Zhang B, Gao L, Tao K, Li Q, Sun J L, Yan Q 2023Nature Communications 144398

    [18]

    He S, Liu D, Zhang G, Chu F, Xu G, Li G, Liu J, Yang Y, Zhang Y 2024ACS omega 9 43368

    [19]

    Du L, Zhao Y, Wu L, Hu X, Yao L, Wang Y, Bai X, Dai Y, Qiao J, Uddin M G, Li X 2021Nature Communications 12 4822

    [20]

    Chu F, Zhou W, Zhou R, Li S, Liu D, Zheng Z, Li J, Zhang Y 2022J. Phys. Chem. Lett. 13 10778

    [21]

    Lu Y L, Dong S, Li J, Wu Y, Wang L, Zhao H 2020Phys. Chem. Chem. Phys. 2213713

    [22]

    Hu Z, Guo W 2021Small 17 2008004

    [23]

    Wang X, An C, Zhang S, Wang S, Li J, Zhu Y 2024Separation and Purification Technology 340126733

    [24]

    Dai S, Zhou W, Liu Y, Lu Y L, Sun L, Wu P 2018Appl. Surf. Sci. 448 281

    [25]

    Han J N, Huang J M, Cao S G, Li Z H, Zhang Z. H 2023 Acta Phys. Sin. 72 19(in Chinese). (韩佳凝, 黄俊铭, 曹胜果, 李占海, 张振华2023物理学报, 72 19.)

    [26]

    Zhang L, Liu Y, Xu Z, Gao G 20232D Mater. 10 045005

    [27]

    Zhang L, Liu Y, Wu M, Gao G 2025Adv. Funct. Mater. 35 2417857

    [28]

    Huang G, Li K, Luo Y, Zhang Q, Pan Y, Gao H 2024Acta Chim. Sinica 82 314(in Chinese). (黄广峥, 李坤玮, 罗艳楠, 张强, 潘远龙, 高洪2024化学学报82 314.)

    [29]

    Liu H, Cao X, Ding L X, Wang H 2022Adv. Funct. Mater. 32 2111161

    [30]

    Hu H, Shi Z, Khan K, Cao R, Liang W, Tareen A K, Zhang Y, Huang W, Guo Z, Luo X, Zhang H 2020J. Mater. Chem. A 8 5421

    [31]

    Lu Y L, Dong S, He H, Li J, Wang X, Zhao H, Wu P 2019Comput. Mater. Sci. 163 209

    [32]

    Lu Y L, Dong S J, Cui F C, Zhang K C, Liu C M, Li J S, Zhuo M 2024 Acta Phys. Sin. 73 016301(in Chinese). (卢一林, 董盛杰, 崔方超, 张开成, 刘春梅, 李杰森, 毛卓2024物理学报73 016301)

    [33]

    Lu Y L, Dong S, Cui F, Zhang K, Liu C, Li J, Mao Z 2025Int. J. Hydrogen Energy 101 222-233

    [34]

    Lu Y L, Dong S, Li J, Wu Y, Zhao H 2022Physica E 138115068

    [35]

    He Q, Wang D D, Qiu H, Si N, Yuan Q, Wang R, Liu S, Wang Y 2024ACS nano 19427

    [36]

    Zhao X, Gu M, Zhai R, Zhang Y, Jin M, Wang Y, Li J, Cheng Y, Xiao B, Zhang J 2023Small 19 2302859

    [37]

    Kresse G, Hafner J 1993Phys. Rev. B 47 R558

    [38]

    Kresse G, Hafner J 1994Phys. Rev. B 4914251

    [39]

    Blochl P E 1994Phys. Rev. B 50 17953

    [40]

    Perdew J P, Burke K, Ernzerhof M 1996Phys. Rev. Lett. 773865.

    [41]

    Monkhorst H J, Pack J D 1976Phys. Rev. B 135188

    [42]

    Grimme S 2006 J. Comput. Chem. 27 1787

    [43]

    Heyd J, Scuseria G E, Ernzerhof M 2003J. Chem. Phys. 118 8207

    [44]

    Ruck M, Hoppe D, Wahl B, Simon P, Wang Y, Seifert G 2005Angew. Chem. Int Ed. 447616

    [45]

    Zhang B, Mao Z, Wu P 2021Appl. Surf. Sci. 565 150546

    [46]

    Casolo S, Lovvik O M, Martinazzo R, Tantardini G F 2009J. Chem. Phys. 130 10

    [47]

    Kulish V V, Malyi O I, Persson C, Wu P 2015Phys. Chem. Chem. Phys. 17 992

    [48]

    Eftekhari A 2017Int. J. Hydrogen Energy 42 11053

    [49]

    Nørskov J K, Bligaard T, Logadottir A, Kitchin J R, Chen J G, Pandelov S, Stimming U 2005J. Electrochem. Soc. 152 J23

    [50]

    Zhao Y, Ma D, Zhang J, Lu Z, Wang Y 2019Phys. Chem. Chem. Phys. 21 20432

    [51]

    Yuan J, Wang C, Liu Y, Wu P, Zhou W 2018J Phys Chem C 123 526

    [52]

    Zhou S, Yang X, Pei W, Liu N, Zhao J 2018Nanoscale 1010876

    [53]

    Pei W, Zhou S, Bai Y, Zhao J 2018Carbon 133 260

    [54]

    Yuan J, Wang C, Liu Y, Wu P, Zhou W 2018 J Phys Chem C 123 526

    [55]

    Nørskov J K, Bligaard T, Logadottir A, Kitchin J R, Chen J G, Pandelov S, Stimming U 2005J Electrochem Soc 152J23

    [56]

    Tsai C, Abild-Pedersen F, Nørskov J K 2014Nano Lett 141381

    [57]

    Lu Y L, Dong S J, Cui F C, Bo T T, Mao Z 2025Acta Chim. Sinica 83 377(in Chinese). (卢一林, 董盛杰, 崔方超, 薄婷婷, 毛卓2025化学学报83 377)

    [58]

    Chen Y, Shi T, Liu P, Ma X, Shui L, Shang C, Chen Z, Wang X, Kempa K, Zhou G 2018 J. Mater. Chem. A 6 19167

    [59]

    Liao J, Sa B, Zhou J, Ahuja R, Sun Z 2014J. Phys. Chem. C 118 17594

    [60]

    Liu J, Cheng B, Yu J 2016Phys. Chem. Chem. Phys. 18 31175

    [61]

    Kresse G, Hafner J 1994Phys Rev B 4914251

  • [1] 王坤, 徐鹤嫣, 郑雄, 张海丰. 第一性原理计算研究Cr掺杂CuZr2的电子结构、弹性性质和硬度. 物理学报, doi: 10.7498/aps.74.20250264
    [2] 胡军平, 梁丝思, 段惠贤, 田俊程, 陈硕, 戴柏杨, 黄春来, 刘宇, 吕营, 万利佳, 欧阳楚英. 氮氧锚定的单原子铜掺杂石墨烯作为碱离子电池负极的理论预测研究. 物理学报, doi: 10.7498/aps.74.20241461
    [3] 万煜炜, 王瑞, 周文权, 王一平, 蔡亚楠, 王常. Ag, Cu掺杂氧化石墨烯吸附NH3的第一性原理研究. 物理学报, doi: 10.7498/aps.74.20241737
    [4] 雷雪玲, 朱巨湧, 柯强, 欧阳楚英. 第一性原理研究硼掺杂氧化石墨烯对过氧化锂氧化反应的催化机理. 物理学报, doi: 10.7498/aps.73.20240197
    [5] 张小娅, 宋佳讯, 王鑫豪, 王金斌, 钟向丽. In掺杂h-LuFeO3光吸收及极化性能的第一性原理计算. 物理学报, doi: 10.7498/aps.70.20201287
    [6] 王逸飞, 李晓薇. 石墨烯/BiOI纳米复合物电子结构和光学性质的第一性原理模拟计算. 物理学报, doi: 10.7498/aps.67.20172220
    [7] 戚玉敏, 陈恒利, 金朋, 路洪艳, 崔春翔. 第一性原理研究Mn和Cu掺杂六钛酸钾(K2Ti6O13)的电子结构和光学性质. 物理学报, doi: 10.7498/aps.67.20172356
    [8] 贾婉丽, 周淼, 王馨梅, 纪卫莉. Fe掺杂GaN光电特性的第一性原理研究. 物理学报, doi: 10.7498/aps.67.20172290
    [9] 李聪, 郑友进, 付斯年, 姜宏伟, 王丹. 稀土(La/Ce/Pr/Nd)掺杂锐钛矿相TiO2磁性及光催化活性的第一性原理研究. 物理学报, doi: 10.7498/aps.65.037102
    [10] 朱玥, 李永成, 王福合. Li掺杂对MgH2(001)表面H2分子扩散释放影响的第一性原理研究. 物理学报, doi: 10.7498/aps.65.056801
    [11] 嘉明珍, 王红艳, 陈元正, 马存良, 王辉. Al, Fe, Mg掺杂Li2MnSiO4的电子结构和电化学性能的第一性原理研究. 物理学报, doi: 10.7498/aps.64.087101
    [12] 徐晶, 梁家青, 李红萍, 李长生, 刘孝娟, 孟健. Ti掺杂NbSe2电子结构的第一性原理研究. 物理学报, doi: 10.7498/aps.64.207101
    [13] 廖建, 谢召起, 袁健美, 黄艳平, 毛宇亮. 3d过渡金属Co掺杂核壳结构硅纳米线的第一性原理研究. 物理学报, doi: 10.7498/aps.63.163101
    [14] 王涛, 陈建峰, 乐园. I掺杂金红石TiO2(110)面的第一性原理研究. 物理学报, doi: 10.7498/aps.63.207302
    [15] 张学军, 张光富, 金辉霞, 朱良迪, 柳清菊. N, Co共掺杂锐钛矿相TiO2光催化剂的第一性原理研究. 物理学报, doi: 10.7498/aps.62.017102
    [16] 曹娟, 崔磊, 潘靖. V,Cr,Mn掺杂MoS2磁性的第一性原理研究. 物理学报, doi: 10.7498/aps.62.187102
    [17] 吴木生, 徐波, 刘刚, 欧阳楚英. Cr和W掺杂的单层MoS2电子结构的第一性原理研究. 物理学报, doi: 10.7498/aps.62.037103
    [18] 李泓霖, 张仲, 吕英波, 黄金昭, 张英, 刘如喜. 第一性原理研究稀土掺杂ZnO结构的光电性质. 物理学报, doi: 10.7498/aps.62.047101
    [19] 梁培, 王乐, 熊斯雨, 董前民, 李晓艳. Mo-X(B, C, N, O, F)共掺杂TiO2体系的光催化协同效应研究. 物理学报, doi: 10.7498/aps.61.053101
    [20] 关丽, 李强, 赵庆勋, 郭建新, 周阳, 金利涛, 耿波, 刘保亭. Al和Ni共掺ZnO光学性质的第一性原理研究. 物理学报, doi: 10.7498/aps.58.5624
计量
  • 文章访问数:  217
  • PDF下载量:  4
  • 被引次数: 0
出版历程
  • 上网日期:  2025-06-18

/

返回文章
返回