As an excellent hydrogen‐storage medium, methanol has many advantages, such as high hydrogen content (12.6 wt %), low cost, and availability from biomass or photocatalysis. However, conventional methanol–water reforming usually proceeds at high temperatures. In this research, we successfully designed a new effective strategy to generate hydrogen from methanol at near‐room temperature. The strategy involved two main processes: CH₃OH→HCOOH→H₂ and NADH→HCOOH→H₂. The first process (CH₃OH→HCOOH→H₂) was performed by an alcohol dehydrogenase (ADH), an aldehyde dehydrogenase (ALDH), and an Ir catalyst. The second procedure (NADH→HCOOH→H₂) was performed by formate dehydrogenase (FDH) and the Ir catalyst. The Ir catalyst used was a previously reported polymer complex catalyst [Cp*IrCl₂(ppy); Cp*=pentamethylcyclopentadienyl, ppy=polypyrrole] with high catalytic activity for the decomposition of formic acid at room temperature and is compatible with enzymes, coenzymes, and poisoning chemicals. Our results revealed that the optimum hydrogen generation rate could reach up to 17.8 μmol h⁻¹ g_cat⁻¹ under weak basic conditions at 30 °C. This will have high impact on hydrogen storage, production, and applications and should also provide new inspiration for hydrogen generation from methanol.

中文翻译：

---

室温下借助脱氢酶的甲醇-水水相重整

作为一种出色的氢存储介质，甲醇具有许多优势，例如氢含量高（12.6 wt％），成本低以及可从生物质或光催化中获得。但是，常规的甲醇-水重整通常在高温下进行。在这项研究中，我们成功设计了一种新的有效策略，可以在接近室温的条件下从甲醇制氢。该策略涉及两个主要过程：CH ₃ OH → HCOOH → H ₂和NADH → HCOOH → H ₂。第一个过程（CH ₃ OH → HCOOH → H ₂用醇脱氢酶（ADH），醛脱氢酶（ALDH）和Ir催化剂进行。第二步（NADH → HCOOH → H ₂）是通过甲酸脱氢酶（FDH）和Ir催化剂进行的。所用的Ir催化剂是先前报道的聚合物络合物催化剂[Cp * IrCl ₂（ppy）；Cp * IrCl ₂（ppy）。Cp * =五甲基环戊二烯基，ppy =聚吡咯]，具有在室温下分解甲酸的高催化活性，并且与酶，辅酶和中毒化学物质相容。我们的结果表明，最佳氢生成速率可以达到17.8μmolh ^-1  g _cat ^-1在30°C的弱碱性条件下。这将对氢的存储，生产和应用产生重大影响，并且还将为甲醇制氢提供新的启示。