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Cu负载量对Cu/CeO2催化CO2加氢制甲醇性能的影响

  • 李传
  • ， 谭延芹
  • ， 甘泽
  • ， 何欣颖
  • ， 张世博
  • ， 粟子凌
  • ， 罗辉
  • ， 邓文安
  • ， 杜峰

1. 重质油国家重点实验室（开云电竞投注（华东）），山东青岛 266580；

Effect of Cu loading on performance of Cu/ CeO2 catalysts for CO2 hydrogenation to methanol

  • LI Chuan
  • ， TAN Yanqin
  • ， GAN Ze
  • ， HE Xinying
  • ， ZHANG Shibo
  • ， SU Ziling
  • ， LUO Hui
  • ， DENG Wenan
  • ， DU Feng

1. State Key Laboratory of Heavy Oil Processing, China University of Petroleum（East China）, Qingdao 266580 ，China；

作者简介:

李传（1981-），男，教授，博士，研究方向为重质油化学与加工。E-mail: lichuan@upc.edu.cn。

通信作者:

李传（1981-），男，教授，博士，研究方向为重质油化学与加工。E-mail: lichuan@upc.edu.cn。

文章编号:1673-5005(2026)02-0202-09

DOI:10.3969/j.issn.1673-5005.2026.02.021

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目录contents

    摘要

    研究Cu负载量为10%、20%及30%的Cu/CeO2催化剂对CO2加氢制甲醇性能的影响，采用XRD、BET和CO2-TPD等表征手段，分析Cu负载量对催化剂加氢性能影响的机制。结果表明：Cu负载量（质量分数）为20%的催化剂活性最佳，其在反应温度为240 ℃、反应压力为3 MPa、质量空速为12000 mL/(g·h)以及V(H2)/V(CO2)=3∶1时，CH3OH的选择性和时空收率为85.2%和13.8 g/(kg·h);Cu负载量为20%的催化剂呈现最小CeO2晶格参数和晶粒尺寸，比表面积最大，碱性活性位点数量最多，说明适宜的Cu负载量可增强Cu物种在CeO2载体表面的分散度,增大反应原料与催化剂的接触面积,提高催化剂对CO2分子的吸附能力，从而实现CO2加氢制甲醇反应中Cu/CeO2催化剂催化性能的提升。

    Abstract

    The effects of Cu/ CeO2 catalysts with Cu loading 20% and 30% on the performance of CO2 hydrogenation to methanol were studied. XRD, BET, and CO2-TPD were used to investigate the influence mechanism of Cu loading on the hydrogenation performance of the catalyst. The results show that the catalyst with Cu loading of 20% has the best activity. When the reaction temperature is 240 ℃, the reaction pressure is 3 MPa, the mass space velocity is 12000 mL/(g·h), and V(H2)/V(CO2)=3∶1, the selectivity and spatiotemporal yield of CH3OH are 85.2% and 13.8 g/(kg·h), respectively. The catalyst with Cu loading of 20% shows the smallest lattice parameters and grain size of CeO2, the largest specific surface area, and the largest number of basic active sites. This indicates that an appropriate Cu loading can enhance the dispersion of Cu species on the surface of the CeO2 carrier, increase the contact area between the reaction raw materials and the catalyst, and improve the adsorption capacity of the catalyst for CO2 molecules. Thus, the catalytic performance of the Cu/ CeO2 catalyst in the reaction of CO2 hydrogenation to methanol is improved.

  • 大气中CO2的增加导致包括全球变暖、海平面上升、海洋酸化、其他生态系统受到干扰、野火、洪水、热带风暴等问题[1-4]。CO2的捕集、利用和封存（CCUS）备受关注[4-10]，特别是将CO2转换为甲醇（CH3OH）和甲烷等高附加值产品[11-13]。CH3OH具有易液化、储能密度高、存储和运输安全性高、成本低等优点 [14]，是理想的储能载体之一。通过催化加氢将CO2转化为CH3OH，既能实现氢能的高密度化学储存，又能将工业排放的CO2转化为高附加值化学品，形成“碳捕获—资源化”的闭环路径[15-18]。基于铜[19-23]（Cu）、锌（Zn）、金（Au）等[24-25]金属基催化剂体系在CO2加氢制CH3OH中表现出优异的性能。密度泛函理论（DFT）[26]表明，Cu（111）晶面对HCOO*中间体的形成能垒为0.72 eV，表现出优异的活化能力。传统Cu/ZnO/Al2O3催化剂在240℃下的CH3OH时空收率仅为0.15 g/（g·h），且运行500 h后活性下降约40%，表明其综合性能仍需通过组分优化和结构设计进行提升。通过调变金属氧化物载体和金属之间的相互作用，可实现催化剂性能的可控构筑[27-28]。Wang等[29]在研究中合成Cu/ CeO2和Cu/ZrO2并进行性能测试，结果表明，在3.0 MPa和200~300℃下，这2种催化剂催化性能均优于纯铜催化剂，并且Cu/ CeO2催化剂经历的是碳酸盐反应路径，表现出更高的CH3OH选择性。以CeO2为载体的Cu/ CeO2具有丰富的氧空位与表面活性位点以及工业化应用潜力等优势成为研究热点[30-35]。浸渍法由于其操作简单、适用性广及重复性好等特点广泛应用于催化剂和复合材料的制备。笔者采用过量浸渍法调控活性组分Cu负载量，制备系列Cu/ CeO2催化剂，在固定床反应器上进行活性评价，结合采用多维度表征技术解析催化剂构效关系，探究Cu物种分散度—酸碱特性协同作用与催化性能的之间的关联。

  • 1 试验

  • 1.1 原料和试剂

  • 三水合硝酸铜（AR）购自阿拉丁化学试剂有限公司；六水合硝酸铈（AR）购自麦克林生化科技有限公司；氢氧化钠（AR）购自国药集团化学试剂有限公司；无水乙醇（AR）购自上海泰坦科技股份有限公司。

  • 1.2 催化剂制备方法

  • （1）水热法制备CeO2载体。称取一定量的氢氧化钠和硝酸铈（ n（Ce3+）∶n（OH-）=3∶1），分别溶于去离子水，将NaOH溶液缓慢滴加至硝酸铈溶液中，连续搅拌30 min，将混合物转移至内衬为聚四氟乙烯材质的水热釜中，将水热釜放入120℃烘箱中反应4 h，冷却至室温后将混合物抽滤，用去离子水洗涤至pH=7，在100℃干燥2 h，并以2℃/min的升温速率升至500℃，在500℃焙烧3 h，得到CeO2载体。

  • （2）过量浸渍法制备Cu/ CeO2催化剂。称取适量的Cu（NO3）2·3H2O和CeO2载体，混合后加入无水乙醇，使Cu（NO3）2·3H2O和CeO2载体溶于无水乙醇，在磁力搅拌器中搅拌24 h进行浸渍，浸渍结束后将无水乙醇蒸干，将固体置于烘箱中于100℃干燥2 h，然后置于马弗炉中，以2℃/min的升温速率升至400℃焙烧2 h，即可得到催化剂。

  • 制备3种不同金属Cu负载量的Cu/ CeO2催化剂，分别命名为10% Cu/ CeO2、20% Cu/ CeO2和30% Cu/ CeO2，其中的占比代表催化剂中Cu的质量分数。

  • 1.3 催化剂表征方法

  • 1.3.1 X射线衍射分析（XRD）

  • 采用荷兰帕纳科公司的X-Pertpro MPD型射线粉末衍射仪对催化剂样品进行物相分析和晶型分析。操作参数为：Cu Kα辐射线（λ=1.54 nm），扫描电压40 kV、扫描电流40 mA，步长0.03，扫描范围2θ为10°~75°。

  • 1.3.2 氮气吸脱附分析（BET）

  • 对催化剂进行氮气（N2）吸脱附表征，可通过比表面积及孔隙度分析仪来评估材料的CO2吸附性能、孔隙分布情况并计算样品的BET比表面积。

  • 本试验采用美国Micromertics公司生产的ASPA2020型自动吸附仪进行测定（吸附质为N2，液氮温度-196.15℃），对所合成的催化剂的Brunauer-Emmett-Teller（BET）比表面积和孔径分布大小进行测试分析。

  • 1.3.3 CO2-程序升温吸附（CO2-TPD）

  • 使用美国麦克公司生产的AutoChem HP 2950型化学吸附仪测试催化剂样品对CO2气体吸脱附含量，从而反映催化剂样品的碱性和碱量。

  • 催化剂在300℃下，通10% H2/Ar混合气还原2 h，在50℃下吸附CO2 1 h，10℃/min的升温速率从100℃升到800℃。

  • 1.4 催化剂评价方法

  • 1.4.1 催化剂评价流程

  • 取1.75 g的Cu/ CeO2催化剂进行充分研磨、压片及筛分处理，选取0.425~0.85 mm的颗粒，将颗粒倒入内径为10 mm的不锈钢反应管中，并用石英砂装填在催化剂床层两侧，两段用石英棉固定。通N2试压，检验装置气密性，确认无漏气后，采用10% H2/N2混合气在300℃还原2 h。还原完毕后等待自然冷却至反应温度，通入混合气体（N2、H2、CO2体积比为30∶30∶10）进行CO2加氢反应。催化剂评价装置流程如图1所示。

  • 图1 催化剂评价装置流程图

  • Fig.1 Flow chart of catalyst performance device

  • 1.4.2 产物计算方法

  • 在进行催化剂性能测试中，固定床反应装置出气管线与气相色谱仪相连通，待反应完成后将CO2加氢制CH3OH的反应产物与未进行反应的原料气化通入气相色谱仪进行在线分析，建立色谱分析方法来进行分析计算。原料CO2转化率x（CO2）、目标产物CH3OH的选择性S（CH3OH）、收率y（CH3OH）和时空收率f（CH3OH）计算公式为

  • xCO2=nCO2,in-nCO2, out nCO2,in,
    (1)
  • SCH3OH=nCH3OH, out nCO2, in -nCO2, out ,
    (2)
  • yCH3OH=xCO2SCH3OH,
    (3)
  • fCH3OH=VCO2xCO2SCH3OHMMeOHWcat .
    (4)

  • 式中，n（CO2，in）为反应器入口CO2的物质的量，mol；n（CO2，out）为反应器出口CO2的物质的量，mol；n（CH3OH，out）为反应器出口CH3OH的物质的量，mol；VCO2为反应器入口CO2的摩尔流量，mol/h；MMeOH为CH3OH的摩尔质量，g/mol；Wcat为催化剂的装填质量，g。

  • 1.4.3 反应条件考察

  • 在固定床反应器中进行CO2加氢制CH3OH性能评价，考察反应温度、反应压力、质量空速及反应进料体积比对催化剂加氢活性的影响。低温有利于CH3OH合成，但温度过低会导致反应速率过慢，需在催化剂活性温度范围内；升高压力有利于CO2合成CH3OH，但考虑到经济成本，安全性等因素，压力一般控制在1.0~8.0 MPa；V（H2）/V（CO2）升高有利于CO2加氢合成CH3OH，当反应进料体积比V（H2）/V（CO2）高于4.0时，CH3OH平衡收率基本不再变化。因此性能评价具体工艺参数如下。

  • （1）固定反应条件p=3 MPa、质量空速v（WHSV）=2400 mL/（g·h）、V（H2）/V（CO2）=3∶1，反应温度T为200、220、240、260和280℃；

  • （2）固定反应条件T=240℃、v（WHSV）=2400 mL/（g·h）、V（H2）/V（CO2）=3∶1，p为1、2、3、4、5 MPa；

  • （3）固定反应条件T=240℃、p=3 MPa、V（H2）/V（CO2）=3∶1，v（WHSV）为2400、4800、7200、9600、12000 mL/（g·h）；

  • （4）固定反应条件T=240℃、p=3 MPa、v（WHSV）=2400 mL/（g·h），V（H2）/V（CO2）为1∶1、2∶1、3∶1、4∶1、5∶1。

  • 2 结果分析

  • 2.1 不同Cu负载量对催化剂性能的影响

  • 不同Cu负载量Cu/ CeO2催化剂在不同工艺条件下的CH3OH时空收率如图2所示。

  • 由图2可知，随着温度的增加，CH3OH时空收率呈现先增加后减少的趋势；随着压力和空速的增加，反应活性呈现先增加后稳定的趋势；而随着原料中V（H2）/V（CO2）的增加，产物CH3OH时空收率呈现上升的趋势。在不同的工艺参数条件下，20% Cu/ CeO2催化剂反应效果均优于10% Cu/ CeO2及30% Cu/ CeO2。因此较优工艺条件为T=240℃、p=3 MPa、V（H2）/V（CO2）=3∶1、v（WHSV）=12000 mL/（g·h）。在此工艺条件下，对3种催化剂进行24 h稳定性评价，结果见图3。

  • 由图3可知，随反应时间延长，3种催化剂的CO2转化率基本保持稳定，而CH3OH选择性逐渐下降，在8 h后趋于稳定。20% Cu/ CeO2催化剂的CO2转化率和CH3OH选择性均高于10% Cu/ CeO2及30% Cu/ CeO2。

  • 3 种催化剂在8~24 h稳定阶段的加氢活性见图4。可以看出，20% Cu/ CeO2催化剂具有最优的催化性能。

  • 2.2 不同Cu负载量对催化剂结构的影响

  • 2.2.1 Cu负载量对催化剂晶体结构的影响

  • 不同金属Cu负载量的Cu/ CeO2催化剂的XRD谱图见图5。

  • 由图5可知，所制备的催化剂均有明显的CuO和CeO2的衍射峰，表明CeO2和CuO共存。在2θ=28.5°、33.1°、47.5°、56.3°、59.1°、69.4°的衍射峰分别对应CeO2（JCPDS 81-0792）立方萤石结构的（111）、（200）、（220）、（311）、（222）、（400）晶面；在2θ=35.5°、38.7°的衍射峰对应CuO（JCPDS 80-1917）的（002）、（111）晶面。

  • 图2 催化剂在不同工艺条件下的CH3OH时空收率

  • Fig.2 Spatio-temporal yields of catalysts under different process conditions

  • 图3 催化剂稳定性测试

  • Fig.3 Catalyst stability test

  • 随着Cu负载量的增加，Cu特征峰强度逐渐增大，说明Cu已经负载到CeO2载体上，CeO2的结晶度随着Cu负载量的增加而下降，CeO2的衍射峰半高宽略有变化，表明晶粒尺寸可能有所变化。该结果表明，通过控制Cu的负载量，可以调节Cu/ CeO2催化剂的物相组成和结晶度，从而影响其催化性能。

  • 图4 不同Cu负载量Cu/ CeO2催化剂加氢性能

  • Fig.4 Hydrogenation performance of Cu/ CeO2 catalysts with different Cu loads

  • 采用Scherrer公式计算结果不同Cu负载量的Cu/ CeO2催化剂晶体学数据见表1。

  • 图5 不同Cu负载量Cu/ CeO2催化剂的XRD图

  • Fig.5 XRD patterns of Cu/ CeO2 catalysts with different Cu loadings

  • 表1表明，随着Cu负载量的增加，Cu/ CeO2催化剂中CeO2（111）晶面对应的特征衍射峰位（2θ）呈现向高角度偏移趋势（Δ（2θ）=0.05°~0.10°）。这一现象表明CeO2晶格发生收缩，其（111）晶面间距随Cu负载量的变化呈现线性响应特征。结合文献报道[36-38]的CeO2晶格收缩与阳离子价态变化的关联性，上述结构演变可能归因于Ce4+的部分还原为离子半径较大的Ce3+，此过程引发的晶格畸变可通过氧空位形成机制予以解释[39]。结构参数分析表明，当Cu负载量为20%时，体系呈现最小晶格参数（a=5.410 Å）和最小CeO2晶粒尺寸（d=11.87 nm），其较小的晶粒粒径（小于12 nm）和适度的晶格畸变有利于提升催化活性位点的暴露。

  • 表1 不同Cu负载量的Cu/ CeO2催化剂晶体学数据

  • Table1 Crystallographic data of different-loading Cu/ CeO2 catalysts

  • 2.2.2 Cu负载量对催化剂孔道结构的影响

  • 不同Cu负载量Cu/ CeO2催化剂的N2吸附-脱附等温曲线如图6（a），其对应的BJH孔径分布如图6（b）所示。

  • 图6 不同Cu负载量的Cu/ CeO2催化剂的BET图谱

  • Fig.6 BET profiles of Cu/ CeO2 catalysts with different Cu loadings

  • 由图6可知，当Cu负载量分别为10%、20%和30%时，所有样品均呈现IV型等温线特征，且在相对压力0.4~0.9内出现明显滞后环，这证实了样品具有典型的介孔结构特征。其中，20% Cu/ CeO2催化剂在0.6＜pr＜0.8区间表现出陡峭的吸附分支，结合孔径分布数据显示其主孔道分布在5~15 nm范围，这与其较高的比表面积（26.2 m2/g）和孔容（0.14 cm3/g）相吻合。值得注意的是，20% Cu/ CeO2样品在pr＜0.1区间的吸附量明显增加，结合其孔径分布向3~5 nm区域偏移的特征，推测其孔道结构可能由微孔或较小尺寸的介孔构成。

  • CeO2载体和不同Cu负载量Cu/CeO2催化剂的BET表征结果见表2。可以看出，纯载体CeO2载体的比表面积和孔径最大，随着金属组分Cu负载量从10%增至30%，催化剂的比表面积和孔径呈现先增加后减小趋势，推测是由于Cu在制备过程中发生聚合等堵塞部分载体的孔道，当Cu加入量为20%时催化剂具有最大的比表面积，20% Cu在CeO2上的分散型较好，表面具有更多的活性位点，平均孔径变化不大，说明金属的负载并未改变载体CeO2的孔道结构，较好地保留了载体的较大孔径的优点。

  • 表2 CeO2载体和不同Cu负载量Cu/ CeO2 催化剂的BET表征结果

  • Table2 BET characterization of CeO2 support and Cu/ CeO2 catalysts with different Cu loads

  • 这一系列结构演变表明，Cu物种的引入对CeO2基复合材料的孔结构具有调控作用。当Cu负载量低于20%时，CuO纳米颗粒主要分散在CeO2载体表面，形成开放型介孔结构；而当负载量达到30%时，过量Cu物种可能部分堵塞孔道或导致载体结构塌陷，从而引起比表面积下降和微孔比例增加。

  • 2.2.3 Cu负载量对催化剂碱性强度的影响

  • 不同Cu负载量Cu/ CeO2催化剂的CO2-TPD表征见图7。其中（b）、（c）、（d）是不同Cu负载量Cu/ CeO2催化剂对应的α和β峰拟合图。

  • 图7 不同Cu负载量的Cu/ CeO2催化剂的CO2-TPD图谱

  • Fig.7 CO2-TPD profiles of Cu/ CeO2 catalysts with different Cu loadings

  • 从图7看出，Cu/ CeO2催化剂具有CO2脱附峰，低温记为α峰，高温记为β峰。100℃的峰归属于催化剂表面的吸附的羟基，160℃的峰归属于CuO的CO2脱附峰。随着Cu金属负载量的增加，100℃的脱附峰强度有所下降，推测由于CuO活性位点对羟基的吸附能力增强，不易脱附，当Cu负载量为30% 时该峰几乎消失，这与推测结果相匹配。对于160℃的峰，随着负载量的增加向低温处偏移，说明高负载量更有利于低温CO2的脱附。其中10% Cu/ CeO2和20% Cu/ CeO2的β脱附峰温度接近，但20% Cu/ CeO2拥有较大的CO2脱附量，说明20% Cu/ CeO2催化剂能吸附更多的CO2分子，可以使更多的CO2分子发生反应。

  • 不同Cu负载量Cu/ CeO2催化剂的CO2脱附峰温度和面积见表3。

  • Cu/ CeO2催化剂加氢机制[40]普遍认为H2在Cu粒子上吸附活化，CO2在载体上吸附活化，Cu表面解离的氢通过溢出转运到载体位点表面，并将吸附中间体加氢形成CH3OH。从图7、表3中发现β峰的面积明显大于α峰，说明在催化剂表面起主导作用的为表面碱性位的CO2脱附。其中20% Cu/ CeO2拥有较大的β峰峰面积，说明20% Cu/ CeO2催化剂拥有较多的表面碱性位，因此能吸附更多的CO2分子。

  • 表3 不同Cu负载量Cu/ CeO2催化剂的CO2 脱附峰温度和面积

  • Table3 CO2 desorption peak temperature and area of Cu/ CeO2 with different Cu loads

  • Cu基催化剂催化CO2加氢合成CH3OH的反应温度一般均大于200℃，由于CO2分子结构的特殊性，导致其具有化学惰性，低温难以活化，强碱性位点是吸附活化CO2的有效活性位点，这些强碱性位点对应于催化剂表面的氧空位缺。因此可通过优化各项制备条件以扩大β峰的优势以提高催化剂活性。

  • 3 结论

  • （1）在不同的工艺参数条件下，20% Cu/ CeO2催化剂反应效果均优于10% Cu/ CeO2及30% Cu/ CeO2，且在T=240℃、p=3 MPa、V（H2）/V（CO2）=3∶1、v（WHSV）=12000 mL/（g·h）时，20% Cu/ CeO2催化剂的加氢催化性能最佳，CH3OH选择性最高可达85.2%，时空收率f（CH3OH）最高可达13.8 g/（kg·h）。

  • （2）随着Cu负载量从10%增至30%，Cu特征峰强度逐渐增大，CeO2的结晶度逐渐下降，CeO2（111）晶面对应的特征衍射峰位（2θ）呈现向高角度偏移趋势，表明Cu已经负载到CeO2载体上且CeO2晶格发生收缩；催化剂的比表面积和孔径随着Cu负载量的增加呈现先增加后减小趋势，说明Cu的引入对Cu/ CeO2催化剂的孔结构具有调控作用，为反应提供更多活性中心，进而改善加氢性能；CO2-TPD表征结果表明，随着Cu负载量的增加，CO2低温脱附峰强度有所下降，高温脱附峰向低温处偏移，说明高负载量更有利于低温CO2的脱附。

  • （3）当Cu负载量为20%时，催化剂具有最小晶格参数和CeO2晶粒粒径及最大的比表面积，Cu物种在CeO2载体表面高度分散，暴露出更丰富的表面活性位点，且表面的强碱性位数量较多，显著增强了对CO2分子的吸附能力，使更多的CO2分子活化发生反应，提升了催化剂的反应活性。

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    • [29] WANG W,QU Z,SONG L,et al.CO2 hydrogenation to methanol over Cu/CeO2 and Cu/ZrO2 catalysts:tuning methanol selectivity via metal-support interaction[J].Journal of Energy Chemistry,2020,40:22-30.

    • [30] ZHU J,CIOLCA D,LIU L,et al.Flame synthesis of Cu/ZnO-CeO2 catalysts:synergistic metal-support interactions promote CH3OH selectivity in CO2 hydrogenation[J].ACS Catalysis,2021,11(8):4880-4892.

    • [31] LIU Y,MAO D,YU J,et al.Low-temperature CO oxidation on CuO-CeO2 catalyst prepared by facile one-step solvothermal synthesis:improved activity and moisture resistance via optimizing the activation temperature[J].Fuel,2023,332:126196.

    • [32] FAN L,ZHANG J,MA K,et al.Ceria morphology-dependent Pd-CeO2 interaction and catalysis in CO2 hydrogenation into formate[J].Journal of Catalysis,2021,397:116-127.

    • [33] XIE F,XU S,DENG L,et al.CO2 hydrogenation on Co/CeO2-δ catalyst:morphology effect from CeO2 support[J].International Journal of Hydrogen Energy,2020,45(51):26938-26952.

    • [34] 熊靖,孙彦,马亚肖,等.氧化铈纳米棒负载钯-钴双金属催化甲烷氧化[J].开云电竞投注学报（自然科学版）,2025,49(3):223-231.XIONG Jing,SUN Yan,MA Yaxiao,et al.Methane oxidation catalyzed by Pd-Co bimetallic species supported on CeO2 nanorods[J].Journal of China University of Petroleum(Edition of Natural Science),2025,49(3):223-231.

    • [35] HU X,QIN W,GUAN Q,et al.The synergistic effect of CuZnCeOx in controlling the formation of methanol and CO from CO2 hydrogenation[J].ChemCatChem,2018,10(19):4438-4449.

    • [36] DIVINS N J,KORDUS D,TIMOSHENKO J,et al.Operando high-pressure investigation of size-controlled CuZn catalysts for the methanol synthesis reaction[J].Nature Communications,2021,12(1):1435.

    • [37] WANG X,LIU Y,WANG Z,et al.[Ce3+-OV-Ce4+] located surface-distributed sheet Cu-Zn-Ce catalysts for methanol production by CO2 hydrogenation[J].Langmuir,2024,40(29):15140-15149.

    • [38] ZHANG W,WANG S,GUO S,et al.Effective conversion of CO2 into light olefins along with generation of low amounts of CO[J].Journal of Catalysis,2022,413:923-933.

    • [39] 徐敏杰,朱明辉,陈天元,等.CO2高值化利用：CO2加氢制甲醇催化剂研究进展[J].化工进展,2021,40(2):565-576.XU Minjie,ZHU Minghui,CHEN Tianyuan,et al.High value utilization of CO2:research progress of catalyst for hydrogenation of CO2 to methanol[J].Chemical Industry and Engineering Progress,2021,40(2):565-576.

    • [40] SINGH R,TRIPATHI K,PANT K K.Investigating the role of oxygen vacancies and basic site density in tuning methanol selectivity over Cu/CeO2 catalyst during CO2 hydrogenation[J].Fuel,2021,303:121289.

  • 基本信息

    DOI: 10.3969/j.issn.1673-5005.2026.02.021
    文章编号: 1673-5005(2026)02-0202-09

    基金信息

    山东省自然科学基金面上项目（ZR2022MB116）；

    引用信息

    稿件历史

    收稿日期: 2025-11-20

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