硫掺杂铁基单原子催化剂结构与催化活性的密度泛函理论研究

蔺何; 张禹; 刘晨帆; 蔡璇璇

doi:10.13568/j.cnki.651094.651316.2023.07.19.0001

您当前的位置：

首页 >

文章列表页 >

硫掺杂铁基单原子催化剂结构与催化活性的密度泛函理论研究

更新时间：2026-01-21

- 硫掺杂铁基单原子催化剂结构与催化活性的密度泛函理论研究
- Journal of Xinjiang University (Natural Science Edition in Chinese and English) Vol. 41, Issue 2, Pages: 228-235(2024)
- 作者机构：
  
  新疆大学化学学院省部共建碳基能源资源化学与利用国家重点实验室
- 作者简介：
- 基金信息：
- DOI：10.13568/j.cnki.651094.651316.2023.07.19.0001
  CLC： O643.36;O641.1
- Published：2024
- 稿件说明：
移动端阅览
[1]蔺何,张禹,刘晨帆,等.硫掺杂铁基单原子催化剂结构与催化活性的密度泛函理论研究[J].新疆大学学报(自然科学版)(中英文),2024,41(02):228-235.
[1]蔺何,张禹,刘晨帆,等.硫掺杂铁基单原子催化剂结构与催化活性的密度泛函理论研究[J].新疆大学学报(自然科学版)(中英文),2024,41(02):228-235. DOI： 10.13568/j.cnki.651094.651316.2023.07.19.0001.

DOI：10.13568/j.cnki.651094.651316.2023.07.19.0001.

摘要

通过密度泛函理论计算研究了硫原子掺杂对铁基单原子催化剂结构稳定性和催化活性的影响．采用结构优化和自由能计算的方法，评估了硫掺杂构型的热力学和电化学稳定性．结果表明：硫原子呈卫星式排布环绕单原子催化剂活性位点，形成稳定的催化剂结构，并对活性位点的电子结构进行调控．进一步比较了硫掺杂前后的催化活性，结果显示硫掺杂能够显著降低氧还原反应的过电势，特别是对称性破缺的体系表现出最低的过电势．

Abstract

The impact of sulfur(S) atoms doping on the structural stability and catalytic activity of iron-based single-atom catalysts was investigated using density functional theory calculations. Structural optimization and free energy calculations were employed to assess the thermodynamic and electrochemical stability of the S-doped configurations. The results demonstrated that S atoms adopted a satellite-like arrangement surrounding the active sites of the single-atom catalyst

leading to a stable catalyst structure and modulation of the electronic structure of the active sites. Furthermore

a comparison was made between the catalytic activities of the pristine catalyst and the S-doped catalysts

revealing a significant reduction in the overpotential of the oxygen reduction reaction upon S doping

particularly in systems with broken symmetry.

关键词

Keywords

references

DAVIS S J,LEWIS N S,SHANER M,et al.Net-zero emissions energy systems[J].Science,2018,360(6396):eaas9793.

CHU S,MAJUMDAR A.Opportunities and challenges for a sustainable energy future[J].Nature,2012,488:294-303.

ZHU Y Z,SOKOLOWSKI J,SONG X C,et al.Engineering local coordination environments of atomically dispersed and heteroatom-coordinated single metal site electrocatalysts for clean energy-conversion[J].Advanced Energy Materials,2020,10(11):1902844.

WAN C Z,DUAN X F,HUANG Y.Molecular design of single-atom catalysts for oxygen reduction reaction[J].Advanced Energy Materials,2020,10(14):1903815.

CHEN M J,HE Y H,SPENDELOW J S,et al.Atomically dispersed metal catalysts for oxygen reduction[J].ACS Energy Letters,2019,4(7):1619-1633.

ZHANG J C,YANG H B,LIU B.Coordination engineering of single-atom catalysts for the oxygen reduction reaction:A review[J].Advanced Energy Materials,2021,11(3):2002473.

WEI X Q,LUO X,WU N N,et al.Recent advances in synergistically enhanced single-atomic site catalysts for boosted oxygen reduction reaction[J].Nano Energy,2021,84:105817.

GUO X Y,LIN S R,GU J X,et al.Simultaneously achieving high activity and selectivity toward two-electron O2electroreduction:The power of single-atom catalysts[J].ACS Catalysis,2019,9(12):11042-11054.

KATO M,FUJIBAYASHI N,ABE D,et al.Impact of heterometallic cooperativity of iron and copper active sites on electrocatalytic oxygen reduction kinetics[J].ACS Catalysis,2021,11(4):2356-2365.

YUAN K,L¨UTZENKIRCHEN-HECHT D,LI L B,et al.Boosting oxygen reduction of single iron active sites via geometric and electronic engineering:Nitrogen and phosphorus dual coordination[J].Journal of the American Chemical Society,2020,142(5):2404-2412.

WANG L,ZENG Z H,GAO W P,et al.Tunable intrinsic strain in two-dimensional transition metal electrocatalysts[J].Science,2019,363(6429):870-874.

DONG J C,ZHANG X G,BRIEGA-MARTOS V,et al.In situ Raman spectroscopic evidence for oxygen reduction reaction intermediates at platinum single-crystal surfaces[J].Nature Energy,2019,4(1):60-67.

XU H,WANG D,YANG P X,et al.Atomically dispersed M-N-C catalysts for the oxygen reduction reaction[J].Journal of Materials Chemistry A,2020,8(44):23187-23201.

JIANG R,LI L,SHENG T,et al.Edge-site engineering of atomically dispersed Fe-N4by selective C-N bond cleavage for enhanced oxygen reduction reaction activities[J].Journal of the American Chemical Society,2018,140(37):11594-11598.

LIU Z,SUN F,GU L,et al.Post iron decoration of mesoporous nitrogen-doped carbon spheres for efficient electrochemical oxygen reduction[J].Advanced Energy Materials,2017,7(22):1701154.

ZHU C Z,SHI Q R,XU B Z,et al.Hierarchically porous M-N-C(M=Co and Fe)single-atom electrocatalysts with robust MNx active moieties enable enhanced ORR performance[J].Advanced Energy Materials,2018,8(29):1801956.

ZHAO C X,LI B Q,LIU J N,et al.Intrinsic electrocatalytic activity regulation of M-N-C single-atom catalysts for the oxygen reduction reaction[J].Angewandte Chemie(International Edition in English),2021,60(9):4448-4463.

FU X G,LI N,REN B H,et al.Tailoring FeN4sites with edge enrichment for boosted oxygen reduction performance in proton exchange membrane fuel cell[J].Advanced Energy Materials,2019,9(11):1803737.

DING S C,LYU Z Y,ZHONG H,et al.An ion-imprinting derived strategy to synthesize single-atom iron electrocatalysts for oxygen reduction[J].Small,2021,17(16):e2004454.

ZHANG N,ZHOU T P,CHEN M L,et al.High-purity pyrrole-type FeN4sites as a superior oxygen reduction electrocatalyst[J].Energy&Environmental Science,2020,13(1):111-118.

LI J Z,ZHANG H G,SAMARAKOON W,et al.Thermally driven structure and performance evolution of atomically dispersed FeN4sites for oxygen reduction[J].Angewandte Chemie(International Edition in English),2019,58(52):18971-18980.

QIAO M F,WANG Y,WANG Q,et al.Hierarchically ordered porous carbon with atomically dispersed FeN4for ultraefficient oxygen reduction reaction in proton-exchange membrane fuel cells[J].Angewandte Chemie(International Edition in English),2020,59(7):2688-2694.

WANG X X,PRABHAKARAN V,HE Y H,et al.Iron-free cathode catalysts for proton-exchange-membrane fuel cells:Cobalt catalysts and the peroxide mitigation approach[J].Advanced Materials,2019,31(31):1805126.

KUMAR K,DUBAU L,MERMOUX M,et al.On the influence of oxygen on the degradation of Fe-N-C catalysts[J].Angewandte Chemie(International Edition in English),2020,59(8):3235-3243.

CHEN M J,LI X,YANG F,et al.Atomically dispersed MnN4catalysts via environmentally benign aqueous synthesis for oxygen reduction:Mechanistic understanding of activity and stability improvements[J].ACS Catalysis,2020,10(18):10523-10534.

GAO J,YANG H B,HUANG X,et al.Enabling direct H2O2production in acidic media through rational design of transition metal single atom catalyst[J].Chem,2020,6(3):658-674.

LUO E G,ZHANG H,WANG X,et al.Single-atom Cr-N4sites designed for durable oxygen reduction catalysis in acid media[J].Angewandte Chemie(International Edition in English),2019,58(36):12469-12475.

LI F,HAN G F,NOH H J,et al.Boosting oxygen reduction catalysis with abundant copper single atom active sites[J].Energy&Environmental Science,2018,11(8):2263-2269.

LI J,CHEN S G,YANG N,et al.Ultrahigh-loading zinc single-atom catalyst for highly efficient oxygen reduction in both acidic and alkaline media[J].Angewandte Chemie(International Edition in English),2019,58(21):7035-7039.

CHEN Z G,GONG W B,LIU Z B,et al.Coordination-controlled single-atom tungsten as a non-3D-metal oxygen reduction reaction electrocatalyst with ultrahigh mass activity[J].Nano Energy,2019,60:394-403.

ZHANG J Q,ZHAO Y F,CHEN C,et al.Tuning the coordination environment in single-atom catalysts to achieve highly efficient oxygen reduction reactions[J].Journal of the American Chemical Society,2019,141(51):20118-20126.

HOLBY E F,ZELENAY P.Linking structure to function:The search for active sites in non-platinum group metal oxygen reduction reaction catalysts[J].Nano Energy,2016,29:54-64.

GRAU-CRESPO R,HAMAD S,CATLOW C A,et al.Symmetry-adapted configurational modelling of fractional site occupancy in solids[J].Journal of Physics:Condensed Matter,2007,19(25):256201.

GARCES-PINEDA F A,NGUYEN H C,BLASCO-AHICART M,et al.Push-pull electronic effects in surface-active sites enhance electrocatalytic oxygen evolution on transition metal oxides[J].ChemSusChem,2021,14(6):1595-1601.

AMORES M,EL-SHINAWI H,MCCLELLAND I,et al.Li1.5La1.5MO6(M=W6+,Te6+)as a new series of lithium-rich double perovskites for all-solid-state lithium-ion batteries[J].Nature Communications,2020,11:6392.

YANG H,SAVORY C N,MORGAN B J,et al.Chemical trends in the lattice thermal conductivity of Li(Ni,Mn,Co)O2(NMC)battery cathodes[J].Chemistry of Materials,2020,32(17):7542-7550.

YUWONO J A,BURR P,GALVIN C,et al.Atomistic insights into lithium storage mechanisms in anatase,rutile,and amorphous TiO2electrodes[J].ACS Applied Materials&Interfaces,2021,13(1):1791-1806.

AZIZIHA M,AKBARSHAHI S,PITTALA S,et al.Identification of a Fe-dependent optical mode in CuAl1-x Fex O2[J].The Journal of Physical Chemistry C,2021,125(6):3577-3583.

KIM S,EOM T,HA Y S,et al.Thermodynamics of multicomponent perovskites:A guide to highly efficient and stable solar cell materials[J].Chemistry of Materials,2020,32(10):4265-4272.

KRESSE G,FURTHM¨ULLER J.Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set[J].Physical Review B,Condensed Matter,1996,54(16):11169-11186.

KRESSE G,FURTHM¨ULLER 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.

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

KRESSE G,JOUBERT D.From ultrasoft pseudopotentials to the projector augmented-wave method[J].Physical Review B,1999,59(3):1758-1775.

BL¨OCHL P E.Projector augmented-wave method[J].Physical Review B,Condensed Matter,1994,50(24):17953-17979.

NOH S H,SEO M H,SEO J K,et al.First principles computational study on the electrochemical stability of Pt-Co nanocatalysts[J].Nanoscale,2013,5(18):8625-8633.

ZITOLO A,GOELLNER V,ARMEL V,et al.Identification of catalytic sites for oxygen reduction in iron-and nitrogen-doped graphene materials[J].Nature Materials,2015,14(9):937-942.

GREELEY J,N?RSKOV J K.Electrochemical dissolution of surface alloys in acids:Thermodynamic trends from first-principles calculations[J].Electrochimica Acta,2007,52(19):5829-5836.

N?RSKOV J K,ROSSMEISL J,LOGADOTTIR A,et al.Origin of the overpotential for oxygen reduction at a fuel-cell cathode[J].The Journal of Physical Chemistry B,2004,108(46):17886-17892.

PETERSON A A,ABILD-PEDERSEN F,STUDT F,et al.How copper catalyzes the electroreduction of carbon dioxide into hydrocarbon fuels[J].Energy&Environmental Science,2010,3(9):1311-1315.

HANSEN H A,VISWANATHAN V,N?RSKOV J K.Unifying kinetic and thermodynamic analysis of 2e–and 4e–reduction of oxygen on metal surfaces[J].The Journal of Physical Chemistry C,2014,118(13):6706-6718.

JUNG E,SHIN H,HOOCH ANTINK W,et al.Recent advances in electrochemical oxygen reduction to H2O2:Catalyst and cell design[J].ACS Energy Letters,2020,5(6):1881-1892.

KULKARNI A,SIAHROSTAMI S,PATEL A,et al.Understanding catalytic activity trends in the oxygen reduction reaction[J].Chemical Reviews,2018,118(5):2302-2312.

VISWANATHAN V,HANSEN H A,ROSSMEISL J,et al.Universality in oxygen reduction electrocatalysis on metal surfaces[J].ACS Catalysis,2012,2(8):1654-1660.

LIU Q,WANG X X,LI L,et al.Design of platinum single-atom doped metal nanoclusters as efficient oxygen reduction electrocatalysts by coupling electronic descriptor[J].Nano Research,2022,15(8):7016-7025.

Views

411

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

GaAs掺Mn材料的局域电子结构和磁性

A_nC₂(A=Fe,Co,Ni,Cu)团簇的密度泛函研究(英文)

团簇Co_3NiB₂的反应活性研究

V取代NiMn_2O₄温度依赖电子转移机制的密度泛函理论研究

Related Author

蔺何

段海明

张军

曹彪炳

段海明

秦渝

方志刚

张伟

Related Institution

新疆大学物理系,新疆大学物理系,新疆大学物理系新疆乌鲁木齐830046,新疆乌鲁木齐830046

新疆大学物理科学与技术学院

辽宁科技大学化学工程学院

新疆理化技术研究所

西南科技大学环境与资源学院

⁰