催化学报

催化学报 ›› 2026, Vol. 86: 149-159.DOI: 10.1016/S1872-2067(26)65039-5

• 论文 • 上一篇    下一篇

制备不同晶相以构建碳酸盐形貌工程促进共热耦合原位加氢

于少康a,1, 董猛a,1, 徐明a,b,*(), 吕一佳a, 彭智洋a, 张卫涛a, 郭大冰a, 王以谢a, 薛振a, 杨宇森a,c,*(), 李浩a, 邵明飞a,c,*()   

  1. a 北京化工大学化工资源有效利用国家重点实验室, 北京 100029
    b 东北林业大学合成化学与资源利用创新研究中心, 黑龙江哈尔滨 150040
    c 衢州资源化工创新研究院 , 浙江衢州 324000
  • 收稿日期:2025-09-24 接受日期:2026-01-04 出版日期:2026-07-05 发布日期:2026-06-12
  • 通讯作者: *电子信箱：mingxu@nefu.edu.cn (徐明),
    yangyusen@buct.edu.cn (杨宇森),
    shaomf@mail.buct.edu.cn (邵明飞).
  • 作者简介:第一联系人：1共同第一作者.
  • 基金资助:
    基金作者: 国家重点研发计划(2024YFA1509800);国家自然科学基金(22288102);国家自然科学基金(22090031);黑龙江省自然科学基金杰出青年项目(YQ2024B002)

Boosting co-thermal coupled in-situ reduction of morphology- engineered carbonate via preparing distinct crystalline phases

Shaokang Yua,1, Meng Donga,1, Ming Xua,b,*(), Yijia Lva, Zhiyang Penga, Weitao Zhanga, Dabing Guoa, Yixie Wanga, Zhen Xuea, Yusen Yanga,c,*(), Hao Lia, Mingfei Shaoa,c,*()   

  1. a State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
    b College of Chemistry, Chemical Engineering and Resource Utilization, Center for Innovative Research in Synthetic Chemistry and Resource Utilization, Northeast Forestry University, Harbin 150040, Heilongjiang, China
    c Quzhou Institute for Innovation in Resource Chemical Engineering , Quzhou 324000, Zhejiang, China
  • Received:2025-09-24 Accepted:2026-01-04 Online:2026-07-05 Published:2026-06-12
  • About author:First author contact:1Contributed equally to this work.
  • Supported by:
    National Key R&D Program of China(2024YFA1509800);National Natural Science Foundation of China(22288102);National Natural Science Foundation of China(22090031);Heilongjiang Provincial Natural Science Foundation Outstanding Youth Fund project(YQ2024B002)

RichHTML

2

PDF

10

摘要：

水泥、钢铁、耐火材料和电石等过程工业在国民经济发展中发挥着基础支柱作用. 碳酸盐作为这些行业的主要原料, 在热分解生成金属氧化物或复合氧化物的同时会释放大量CO2, 其碳排放占中国工业总排放量的50%以上, 带来严峻的环境挑战. 碳捕集与利用技术可将捕获的CO2转化为高附加值化学品, 作为一种具有前景的碳减排途径广受关注. 然而, CO2本身具有热力学稳定性和化学惰性, 需要外界提供大量能量以实现其活化和转化. 亟需创新策略以提高CO2利用过程的效率与可行性. 因此, 开发创新、可持续的碳酸盐热解策略以实现减排降耗、提升技术经济性显得尤为迫切.

碳酸盐共热耦合原位还原是一种具有前景的生产金属氧化物并联产合成气的策略, 不仅能促进CO2转化为高附加值化学品, 还可降低热分解温度. 然而, CaCO3形貌调控对其加氢性能与反应机制的影响尚未明确. 本研究通过共沉淀方法制备不同CaCO3晶相, 首次报道了构建形貌工程化CaCO3 (菱形的方解石、球状的球霰石和棒状的文石), 显著增强共热耦合原位还原过程, 大幅降低脱羧温度并实现合成气的高效生成. 研究表明, CaCO3共热耦合原位还原过程强烈依赖于其不同的形貌结构, 同时可制备出具有多种独特形貌的高比表面积的高纯多孔CaO. 通过系统研究不同形貌CaCO3的加氢行为, 发现球形的球霰石在一系列温度下均表现出优于菱形的方解石的加氢性能. 在700 °C时, 球形的球霰石原位加氢的CO选择性为96%, CO生成速率为0.80 mmol min-1, 优于菱形的方解石(分别为95%和0.68 mmol min-1). 相比之下, 棒状的文石在700 °C时CO选择性较低, 为79%; 然而在550 °C的相对较低温度下, 棒状的文石表现出优异的原位加氢性能, CO选择性高达86%, 生成速率为0.46 mmol min-1, 显著超过相同条件下的菱形方解石和球形球霰石, 且其CO生成速率(0.46 mmol min-1)达到球形球霰石的2.3倍以上. 构建CaCO3形貌工程不仅降低了脱羧温度, 也抑制了CO2排放, 实现了CO2向高附加值合成气的高效转化. 此外, 结合程序升温还原-质谱与原位漫反射红外光谱实验, 揭示了CaCO3多形貌的温度依赖性加氢机制, 在相对较低温度时, CO主要通过CaCO3多形貌表面的直接加氢路径生成; 而在较高温度下, 则出现另一条路径—CaCO3热解释放的CO2通过逆水煤气变换反应原位加氢生成气态CO, HCOO*为关键中间物种, 该路径与直接加氢共同介导多形貌CaCO3的原位还原.

综上, 本研究提出了一种制备不同晶相CaCO3以构建形貌工程介导的碳酸钙共热耦合原位加氢新策略, 为开发高效低能耗的CO2转化技术奠定了关键基础, 展现出重要的科学价值和广阔的应用前景.

关键词: 无机碳酸盐, 形貌工程, 晶相, 原位还原, 节能, 减排, 合成气

Abstract:

Co-thermal coupled in-situ hydrogenation of carbonates represents a promising strategy for producing metal oxide coupling syngas, facilitating the CO2 conversion into value-added chemicals while reducing thermal decomposition temperatures. Nevertheless, the impact of CaCO3 morphological modulation on hydrogenation performance and mechanisms has yet to be elucidated. Herein, we first report the morphology-controlled synthesis of CaCO3 with distinct crystalline phases (e.g., rhombohedral calcite, spherical vaterite, and rod-shaped aragonite). This engineered morphology significantly enhances co-thermal coupled in-situ reduction, simultaneously lowering the decarboxylation temperature and promoting syngas formation. Compared with rhombohedral calcite, spherical vaterite exhibits superior CO selectivity and formation rate during reduction processes across various temperatures, reaching 96% and 0.80 mmol min-1 at 700 °C, respectively. Notably, rod-shaped aragonite achieves an exceptional CO selectivity of 86%, surpassing both rhombohedral calcite and spherical vaterite, and the CO formation rate (0.46 mmol min-1) is more than 2.3 times that of spherical vaterite at 550 °C. Moreover, combination of temperature programmed reduction-mass spectrometry and in-situ diffuse reflectance infrared Fourier transformed experiments reveals temperature-dependent hydrogenation mechanisms for different morphologies of CaCO3: direct hydrogenation dominates at relatively low temperatures, while at elevated temperatures, the dual mechanism combining direct hydrogenation and reverse water-gas shift reaction (HCOO* as the key intermediate) prevails. This study presents a novel strategy demonstrating high efficiency and low carbon for sustainable carbonate hydrogenation systems, offering significant scientific merit and industrial potential.

Key words: Inorganic carbonate, Morphology-engineering, Crystalline phase, In-situ reduction, Energy-saving, Emission reduction, Syngas