Effects of trace Zn2+ doping on CO2/CH4 adsorption and separation performances of MIL-101

YANG Hemin; SUN Renjie; WANG Xiangyun; WANG Jianwei; WEI Peng; WANG Lu; TU Jing; SUN Hui

doi:10.12434/j.issn.2097-2547.20260003

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Effects of trace Zn²⁺ doping on CO₂/CH₄ adsorption and separation performances of MIL-101

更新时间：2026-06-02

- Effects of trace Zn²⁺ doping on CO₂/CH₄ adsorption and separation performances of MIL-101
- Pages: 1-12(2026)
- 作者机构：
  
  1.新疆大学化工学院石油天然气精细化工教育部&自治区重点实验室，新疆乌鲁木齐 830046
  2.新疆福克油品股份有限公司，新疆乌鲁木齐 830022
  3.华东理工大学化工学院，上海 200237
- 作者简介：
- 基金信息：
- DOI：10.12434/j.issn.2097-2547.20260003
  CLC： TQ028.2;TQ424
- Received：04 January 2026，
  
  Revised：2026-01-27，
  
  Online First：01 June 2026，
- 稿件说明：
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杨贺敏,孙仁杰,王香云等.微量Zn²⁺掺杂对MIL-101吸附分离CO₂/CH₄性能的影响[J].低碳化学与化工,

YANG Hemin,SUN Renjie,WANG Xiangyun,et al.Effects of trace Zn²⁺ doping on CO₂/CH₄ adsorption and separation performances of MIL-101[J].Low-Carbon Chemistry and Chemical Engineering,
杨贺敏,孙仁杰,王香云等.微量Zn²⁺掺杂对MIL-101吸附分离CO₂/CH₄性能的影响[J].低碳化学与化工, DOI：10.12434/j.issn.2097-2547.20260003.

YANG Hemin,SUN Renjie,WANG Xiangyun,et al.Effects of trace Zn²⁺ doping on CO₂/CH₄ adsorption and separation performances of MIL-101[J].Low-Carbon Chemistry and Chemical Engineering, DOI：10.12434/j.issn.2097-2547.20260003.

摘要

在天然气净化中，为提升金属有机框架材料（MOFs）的CO

/CH

吸附分离性能，采用溶剂热法制备了一系列微量Zn

掺杂的MIL-101材料（Zn-MIL-101）。通过SEM、XRD、FT-IR、ICP-MS、XPS、N

吸/脱附及TG等表征手段对材料的晶体结构、表面化学环境、孔结构及热稳定性进行了表征，并进一步研究了Zn

掺杂对MIL-101吸附分离性能的影响。结果表明，Zn

不是以等量金属节点取代方式进入MIL-101骨架，而是以低含量形式参与金属节点周围的局部配位环境调控，在不破坏框架整体结构的前提下诱导形成一定程度的配位缺陷，从而调变孔道可利用程度及表面化学性质。在298 K、100 kPa的条件下，Zn-M-3（

(硝酸铬):

(硝酸锌) = 5:1）的CO

吸附容量由MIL-101的1.79 mmol/g增至2.72 mmol/g，提高了51.10%，CH

吸附容量则增幅较小。理想吸附溶液理论（IAST）计算结果及CO

/CH

二元混合气体（体积比为20/80）动态吸附实验结果表明，Zn-M-3的CO

/CH

选择性约为MIL-101的1.5倍，且CO

吸附穿透时间延长。密度泛函理论（DFT）计算结果从原子尺度揭示了Zn

掺杂对CO

吸附具有促进作用，对CH

吸附则影响有限。本研究结果揭示了Zn

掺杂诱导的配位环境与孔结构协同调控机制，可为高性能CO

吸附分离材料的设计提供理论依据。

Abstract

To enhance the CO

/CH

adsorption and separation performance of metal-organic framework materials (MOFs) in natural gas purification

a series of MIL-101 materials doped with trace amounts of Zn

(Zn-MIL-101) were synthesized by a solvothermal method. The crystal structure

surface chemical environment

pore structure and thermal stability of the materials were characterized by SEM

XRD

FT-IR

ICP-MS

XPS

adsorption/desorption and TG

and the effects of Zn

doping on the adsorption and separation performance of MIL-101 were further investigated. The results indicate that Zn

does not enter the MIL-101 framework through equivalent metal-node substitution

but instead participates in the regulation of the local coordination environment around the metal nodes at low content

thereby inducing a certain degree of coordination defects without destroying the overall framework structure

and consequently tuning the pore accessibility and surface chemical properties. At 298 K and 100 kPa

the CO

adsorption capacity of Zn-M-3 increases from 1.79 mmol/g for MIL-101 to 2.72 mmol/g

corresponding to an increase of 51.10%

whereas the increase in CH

adsorption capacity is relatively small. The ideal adsorbed solution theory (IAST) calculations and dynamic adsorption experiments of CO

/CH

binary mixed gas (volume ratio of 20/80) show that the CO

/CH

selectivity of Zn-M-3 is approximately 1.5 times that of MIL-101

and the CO

adsorption breakthrough time is prolonged. The density functional theory (DFT) calculation results reveal at the atomic scale that Zn

doping promotes CO

adsorption

whereas its effect on CH

adsorption was limited. The results of this study reveal the synergistic regulation mechanism of coordination environment and pore structure induced by Zn

doping

which can provide a theoretical basis for the design of high-performance CO

adsorption and separation materials.

关键词

Keywords

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