The activity and durability of the Cu/ZnO/Al₂O₃ (CZA) catalyst formulation for methanol synthesis from CO/CO₂/H₂ 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 CO₂ and H₂ alone, making efficient use of sequestered CO₂. 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.

中文翻译：

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Cu/ZnO/Al2O3 基催化剂合成甲醇之谜

用于CO/CO ₂ /H _{2原料合成甲醇的Cu/ZnO/Al 2} O ₃ (CZA)催化剂配方的活性和耐久性远远超过其各个组分的总和。因此，这种三元催化系统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，该系统一直用于甲醇的大规模商业生产，对其原始配方几乎没有任何改变。甲醇是化学工业的关键组成部分。它也是一种有吸引力的储能分子，也可以单独由CO ₂和H ₂产生，从而有效利用封存的CO ₂。因此，这种有些不寻常的催化剂配方在现代化学工业和全球经济领域发挥着巨大的作用，20 世纪 20 年代开始的大量持续研究证明了这一点。然而，尽管取得了商业上的成功，并且旨在了解这种配方如何发挥作用的研究已经持续了几十年，但尚未实现对这种材料如何实现其功效的全面且普遍认同的理解。经过近一个世纪对 CZA 催化剂的研究，本综述的目的是评估迄今为止所取得的成就，并展示该领域的发展方式和程度。为此，本综述按时间顺序评估了有关该催化剂配方的研究，并严格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，该评论试图对当前文献告诉我们的 CZA 催化剂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法。