Beck Arik, Newton Mark A, van de Water Leon G A, van Bokhoven Jeroen A
Institute for Chemistry and Bioengineering, ETH Zurich, 8093 Zürich, Switzerland.
Institute for Chemical Technology and Polymer Chemistry (ITCP), Karlsruhe Institute of Technology (KIT), 76131 Karlsruhe, Germany.
Chem Rev. 2024 Apr 24;124(8):4543-4678. doi: 10.1021/acs.chemrev.3c00148. Epub 2024 Apr 2.
The activity and durability of the Cu/ZnO/AlO (CZA) catalyst formulation for methanol synthesis from CO/CO/H feeds far exceed the sum of its individual components. As such, this ternary catalytic system is a prime example of synergy in catalysis, one that has been employed for the large scale commercial production of methanol since its inception in the mid 1960s with precious little alteration to its original formulation. Methanol is a key building block of the chemical industry. It is also an attractive energy storage molecule, which can also be produced from CO and H alone, making efficient use of sequestered CO. As such, this somewhat unusual catalyst formulation has an enormous role to play in the modern chemical industry and the world of global economics, to which the correspondingly voluminous and ongoing research, which began in the 1920s, attests. Yet, despite this commercial success, and while research aimed at understanding how this formulation functions has continued throughout the decades, a comprehensive and universally agreed upon understanding of how this material achieves what it does has yet to be realized. After nigh on a century of research into CZA catalysts, the purpose of this Review is to appraise what has been achieved to date, and to show how, and how far, the field has evolved. To do so, this Review evaluates the research regarding this catalyst formulation in a chronological order and critically assesses the validity and novelty of various hypotheses and claims that have been made over the years. Ultimately, the Review attempts to derive a holistic summary of what the current body of literature tells us about the fundamental sources of the synergies at work within the CZA catalyst and, from this, suggest ways in which the field may yet be further advanced.
用于由CO/CO/H原料合成甲醇的Cu/ZnO/AlO（CZA）催化剂配方的活性和耐久性远远超过其各组分的总和。因此，这种三元催化体系是催化协同作用的一个典型例子，自20世纪60年代中期问世以来，它一直被用于甲醇的大规模商业生产，其原始配方几乎没有改变。甲醇是化学工业的关键基石。它也是一种有吸引力的储能分子，也可以仅由CO和H生产，从而有效利用封存的CO。因此，这种有点不寻常的催化剂配方在现代化学工业和全球经济领域中发挥着巨大作用，始于20世纪20年代的相应大量且持续的研究证明了这一点。然而，尽管取得了商业成功，并且数十年来旨在理解这种配方如何起作用的研究一直在继续，但对于这种材料如何实现其功能，尚未达成全面且普遍认可的理解。在对CZA催化剂进行了近一个世纪的研究之后，本综述的目的是评估迄今为止所取得的成果，并展示该领域是如何发展以及发展到了什么程度。为此，本综述按时间顺序评估了关于这种催化剂配方的研究，并批判性地评估了多年来提出的各种假设和主张的有效性和新颖性。最终，本综述试图对当前文献所告诉我们的关于CZA催化剂中协同作用的基本来源进行全面总结，并据此提出该领域可能进一步发展的方向。
