Biosynthesis Parameters Control the Physicochemical and Catalytic Properties of Microbially Supported Pd Nanoparticles
Biosynthesis Parameters Control the Physicochemical and Catalytic Properties of Microbially Supported Pd Nanoparticles
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DOI：
10.1002/smll.202311016
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发表时间：
2024-03-10
期刊：
影响因子：
13.3
通讯作者：
Lloyd，Jonathan R.
中科院分区：
文献类型：
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作者：
Morriss，Christopher Egan;Cheung，Casey K.;Lloyd，Jonathan R.
微生物负载钯纳米粒子的生物合成是通过在环境条件下使用廉价的缓冲液和电子供体，如有机酸或氢气，将Pd(II)还原为Pd(0)来实现的。可持续生物钯催化剂是C-C偶联和加氢反应的有效催化剂，但其工业应用受到纳米颗粒性能控制挑战的限制。在这里，以金属还原菌-硫还原地杆菌为例，研究了在不同的Pd负载量和不同的电子供体(醋酸盐、甲酸盐、氢、NO-−供体)下合成生物Pd对纳米颗粒大小、Pd(II)：Pd(0)比和细胞位置等关键性质的影响。控制纳米粒子的大小和位置控制了Bio-Pd还原4-硝基苯酚的活性，而细胞上高的Pd负载量可以合成高活性的Bio-Pd，与商用Pd/C相当，用于Suzuki-Miyaura偶联反应。此外，本研究还证明了由于生物吸附的Pd(II)在重碳酸盐缓冲溶液中的水解，合成了微生物负载的≈2纳米PdO纳米粒子。与商用Pd/C催化剂相比，生物PdO纳米粒子在4-硝基苯酚还原反应中表现出更好的活性。总体而言，控制生物合成参数，如电子供体、金属负载和溶液化学，能够定制生物钯的物理化学和催化性能。
The biosynthesis of Pd nanoparticles supported on microorganisms (bio‐Pd) is achieved via the enzymatic reduction of Pd(II) to Pd(0) under ambient conditions using inexpensive buffers and electron donors, like organic acids or hydrogen. Sustainable bio‐Pd catalysts are effective for C‐C coupling and hydrogenation reactions, but their industrial application is limited by challenges in controlling nanoparticle properties. Here, using the metal‐reducing bacteriumGeobacter sulfurreducens, it is demonstrated that synthesizing bio‐Pd under different Pd loadings and utilizing different electron donors (acetate, formate, hydrogen, no e−donor) influences key properties such as nanoparticle size, Pd(II):Pd(0) ratio, and cellular location. Controlling nanoparticle size and location controls the activity of bio‐Pd for the reduction of 4‐nitrophenol, whereas high Pd loading on cells synthesizes bio‐Pd with high activity, comparable to commercial Pd/C, for Suzuki–Miyaura coupling reactions. Additionally, the study demonstrates the novel synthesis of microbially‐supported ≈2 nm PdO nanoparticles due to the hydrolysis of biosorbed Pd(II) in bicarbonate buffer. Bio‐PdO nanoparticles show superior activity in 4‐nitrophenol reduction compared to commercial Pd/C catalysts. Overall, controlling biosynthesis parameters, such as electron donor, metal loading, and solution chemistry, enables tailoring of bio‐Pd physicochemical and catalytic properties.