氨水改性活性炭/炭黑强化甲烷裂解制氢

李宁宁; 王崇萱; 李欣然; 杨丽; 刘方; 王晨凯; 蒋书闻

doi:10.16085/j.issn.1000-6613.2026-0253

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氨水改性活性炭/炭黑强化甲烷裂解制氢

能源加工与技术 | 更新时间：2026-05-05

- 氨水改性活性炭/炭黑强化甲烷裂解制氢
- Ammonia water-modified activated carbon/carbon black for enhanced hydrogen production via methane cracking
- 化工进展 2026年
- 作者机构：
  
  中国矿业大学低碳能源与动力工程学院，江苏徐州 221116
- 作者简介：
  
  李宁宁（1996—），女，博士研究生，研究方向为甲烷裂解制氢。E-mail: tb24130010p41@cumt.edu.cn。
  杨丽，教授，博士生导师，研究方向为化学链制氢，锂电池回收，二氧化碳捕集与利用。E-mail: Li.yang@cumt.edu.cn
  刘方，教授，博士生导师，研究方向为化学链碳捕集技术、低浓度瓦斯减排及利用、低碳制氢、氮氧化物减排。E-mail: fang.liu@cumt.edu.cn。
- 基金信息：
  
  国家重点研发计划(2023YFE0120600);江苏省自然科学基金(BK20240208)
- DOI：10.16085/j.issn.1000-6613.2026-0253
  中图分类号： TQ53;TK114
- 收稿：2026-02-13，
  
  修回：2026-05-01，
  
  录用：2026-05-02，
- 稿件说明：
移动端阅览
李宁宁, 王崇萱, 李欣然, 等. 氨水改性活性炭/炭黑强化甲烷裂解制氢[J/OL]. 化工进展, 2026.

LI Ningning, WANG Chongxuan, LI Xinran, et al. Ammonia water-modified activated carbon/carbon black for enhanced hydrogen production via methane cracking[J/OL]. Chemical Industry and Engineering Progress, 2026.
李宁宁, 王崇萱, 李欣然, 等. 氨水改性活性炭/炭黑强化甲烷裂解制氢[J/OL]. 化工进展, 2026. DOI： 10.16085/j.issn.1000-6613.2026-0253.

LI Ningning, WANG Chongxuan, LI Xinran, et al. Ammonia water-modified activated carbon/carbon black for enhanced hydrogen production via methane cracking[J/OL]. Chemical Industry and Engineering Progress, 2026. DOI： 10.16085/j.issn.1000-6613.2026-0253.

摘要

针对活性炭催化甲烷裂解（CMD）制氢过程中易失活的瓶颈，提出了一种“化学-物理”复合改性的策略，通过氨水化学改性与炭黑（CB）物理负载相结合，旨在协同提升催化剂的初始活性与长效稳定性。利用多尺度表征技术结合巨正则蒙特卡罗

（GCMC）和密度泛函理论（DFT）模拟，系统阐明了改性催化剂的结构演变规律与稳态接力机制。研究结果表明：5%NH

-A

C-CB 催化剂在950 ℃下展现出卓越的催化稳定性，反应140min后甲烷转化率稳定在38%，较未改性样品提升了约6%。XRD定量拟合证实，反应后积碳产物的C（002）特征峰FWHM从2.083°锐化至0.891°，证实积炭物质实现了从无定形碳向高度石墨化有序碳的转变。XPS结果显示，改性后样品的N1s信号由背景噪声重构为清晰的吡啶-N、吡咯-N与石墨-N 三峰构型，含氮官能团利用强电负性诱导产生Lewis酸位点；同时，改性显著促进了羧基（-COOH）的形成。氨水化学改性成功重构了表面活性微环境。模拟计算证实，各种官能团的添加均可以增加甲烷的吸附量，其中羧基的引入使甲烷最大吸附容量倍增最为明显。炭黑负载通过物理扩孔将平均孔径由2.02nm拓宽至7.70nm。GCMC模拟显示，孔径增大（8–20 Å）使吸附量提升约270%，且大孔径具备更高的吸附能以维持分子吸附稳定性。7.70nm 的介孔通道有效保障了反应物向深层活性位点的持续扩散。研究揭示了催化剂“官能团强化吸附+空隙控传质”的协同机理：氨水改性诱导的异质原子缺陷提供了高效初始活性，而物理孔道保障了定向有序积碳的受控生长，实现了从原始位点向产物结构的活性接力。

Abstract

To address the bottleneck of rapid deactivation in the catalytic methane decomposition (CMD) process over activated carbon for hydrogen production

this study proposes a "chemical-physical" composite modification strategy. By combining chemical modification with ammonia solution and physical loading of carbon black (CB)

the strategy aims to synergistically enhance the initial activity and long-term stability of the catalyst. Multi-scale characterization techniques

coupled with Grand Canonical Monte Carlo (GCMC) and Density Functional Theory (DFT) simulations

were employed to systematically elucidate the structural evolution and steady-state relay mechanism of the modified catalyst. The results indicated that the 5%NH

C-CB catalyst exhibited excellent catalytic stability at 950°C

with a methane conversion rate stabilizing at 38% after 140 minutes of reaction

representing an approximately 6% improvement compared to the pristine sample. Quantitative XRD fitting confirmed that the Full Width at Half Maximum (FWHM) of the C(002) characteristic peak for the deposited carbon after reaction sharpened from 2.083°to 0.891°

verifying the transformation from amorphous carbon to highly graphitized ordered carbon (CNT). XPS results revealed that the modification transformed the N1s signal from background noise into a distinct three-peak

configuration comprising pyridinic-N

pyrrolic-N

and graphitic-N

leveraging their strong electronegativity to induce Lewis acid sites for polarizing C-H bonds. Simultaneously

the modification significantly promoted the formation of carboxyl groups (-COOH). Chemical modification with ammonia successfully reconstructed the surface active microenvironment. Simulation calculations confirmed that the introduction of carboxyl groups doubled the maximum adsorption capacity. Carbon black loading physically expanded the pores

increasing the average pore size from 2.02 nm to 7.70 nm. GCMC simulations demonstrated that the enlargement of pore size (8–20 Å) increased adsorption capacity by approximately 270%

with larger pores exhibiting higher adsorption energy to maintain molecular adsorption stability. The 7.70 nm mesoporous channels effectively ensured the continuous diffusion of reactants to deeper active sites. This study elucidates the synergistic mechanism of "functional group-enhanced adsorption + pore structure-regulated mass transfer": the heteroatomic defects induced by ammonia modification provide efficient initial activity

while the physically tuned pore channels facilitate the controlled growth of oriented and ordered carbon deposits

achieving dynamic activity relay from original sites to product structures.

关键词

Keywords

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