Nickel enrichment of next-generation NMC nanomaterials alters material stability, causing unexpected dissolution behavior and observed toxicity to S. oneidensis MR-1 and D. magna
Nickel enrichment of next-generation NMC nanomaterials alters material stability, causing unexpected dissolution behavior and observed toxicity to S. oneidensis MR-1 and D. magna
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DOI：
10.1039/c9en01074b
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发表时间：
2020-02
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通讯作者：
Joseph T. Buchman;Evan A. Bennett;Chenyu Wang;Ali Abbaspour Tamijani;J. Bennett;Blake G. Hudson;Curtis M. Green;Peter L. Clement;Bo Zhi;Austin H. Henke;E. Laudadio;S. Mason;R. Hamers;R. Klaper;C. Haynes
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作者：
Joseph T. Buchman;Evan A. Bennett;Chenyu Wang;Ali Abbaspour Tamijani;J. Bennett;Blake G. Hudson;Curtis M. Green;Peter L. Clement;Bo Zhi;Austin H. Henke;E. Laudadio;S. Mason;R. Hamers;R. Klaper;C. Haynes
锂插层化合物，如复合金属氧化物，锂镍锰钴氧化物（LiNixMnyCo1−x−yO2，此处简称NMC），已经证明了它们作为储能材料的实用性。为了应对最近对全球钴供应的担忧，工业合成的NMC正在转向使用镍含量丰富的NMC成分。然而，镍是NMC材料中毒性较大的成分之一，值得研究这些材料对环境相关生物的毒性。本研究评估了纳米级和微级富镍纳米mcs对细菌希瓦氏菌MR-1和浮游动物大水蚤的毒性。出乎意料的是，对于细菌来说，尽管每种材料的镍含量不同，但当以相同的表面积剂量使用时，所有NMC材料都表现出相似的毒性。因此，采用密度泛函理论和热力学相结合的方法来模拟材料对有毒物质（即镍和钴离子）的溶解，结果表明，由于富镍材料中含有氧化态>2的镍，材料的稳定性得到了提高。这种材料稳定性的提高意味着富镍NMC和等化学计量NMC之间的溶解性相似，这是在实验中发现的。释放离子的毒性与NMC纳米颗粒的毒性基本一致。对于D. magna，镍的富集增加了NMC的毒性，但这种毒性不是由于离子释放引起的。NMC与野刺草和大刺草均有关联。这项工作表明，对于主要毒性模式是基于离子释放的生物体，在NMC中加入更多的镍不会影响毒性，因为颗粒稳定性增加；然而，对于核心成分决定毒性的生物体，由于纳米颗粒对生物体的特异性影响，在重新设计策略中包括更多的镍可能导致更大的毒性。
Lithium intercalation compounds, such as the complex metal oxide, lithium nickel manganese cobalt oxide (LiNixMnyCo1−x−yO2, herein referred to as NMC), have demonstrated their utility as energy storage materials. In response to recent concerns about the global supply of cobalt, industrially synthesized NMCs are shifting toward using NMC compositions with enriched nickel content. However, nickel is one of the more toxic components of NMC materials, meriting investigation of the toxicity of these materials on environmentally relevant organisms. Herein, the toxicity of both nanoscale and microscale Ni-enriched NMCs to the bacterium, Shewanella oneidensis MR-1, and the zooplankton, Daphnia magna, was assessed. Unexpectedly, for the bacteria, all NMC materials exhibited similar toxicity when used at equal surface area-based doses, despite the different nickel content in each. Material dissolution to toxic species, namely nickel and cobalt ions, was therefore modelled using a combined density functional theory and thermodynamics approach, which showed an increase in material stability due to the Ni-enriched material containing nickel with an oxidation state >2. The increased stability of this material means that similar dissolution is expected between Ni-enriched NMC and equistoichiometric NMC, which is what was found in experiments. For S. oneidensis, the toxicity of the released ions recapitulated toxicity of NMC nanoparticles. For D. magna, nickel enrichment increased the observed toxicity of NMC, but this toxicity was not due to ion release. Association of the NMC was observed with both S. oneidensis and D. magna. This work demonstrates that for organisms where the major mode of toxicity is based on ion release, including more nickel in NMC does not impact toxicity due to increased particle stability; however, for organisms where the core composition dictates the toxicity, including more nickel in the redesign strategy may lead to greater toxicity due to nanoparticle-specific impacts on the organism.