Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity.
Coordination environment tuning of nickel sites by oxyanions to optimize methanol electro-oxidation activity.
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通过氧化对镍位点调整的协调环境调整以优化甲醇电氧化活性。
DOI：
10.1038/s41467-022-30670-4
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发表时间：
2022-05-25
影响因子：
16.6
通讯作者：
中科院分区：
文献类型：
--
作者：
为了实现零碳经济，需要先进的阳极催化剂用于由可再生能源提供动力的制氢和生物质升级。镍基非贵金属电催化剂由于其固有的氧化还原属性而被认为是潜在的候选者，但对镍位配位的深入理解和合理设计仍然具有挑战性。本文通过阳极电化学氧化Ni类金属（NiPx、NiSx和NiSex）原位构建了不同氧阴离子配位的非晶态羟基氧化镍（NiOOH-TOx），其中NiOOH-POx表现出最佳的局部配位环境，提高了Ni位对甲醇选择氧化为甲酸的电催化活性。实验和理论结果表明，NiOOH-POx对OH ~* 和甲醇的吸附性能得到改善，有利于CH_3O ~* 中间体的形成。配位的磷酸根含氧阴离子有效地剪裁了Ni位的d带中心，增加了Ni-O的共价性，提高了催化活性，为含氧阴离子调控活性中心配位环境促进有机分子转化提供了新的思路.在电催化中，金属中心周围的配位环境是重要的。在这里，Ni非金属氧化产生氧阴离子掺杂的非晶Ni-羟基氧化物，其中发现用磷取代以提高甲醇电氧化活性。
To achieve zero-carbon economy, advanced anode catalysts are desirable for hydrogen production and biomass upgrading powered by renewable energy. Ni-based non-precious electrocatalysts are considered as potential candidates because of intrinsic redox attributes, but in-depth understanding and rational design of Ni site coordination still remain challenging. Here, we perform anodic electrochemical oxidation of Ni-metalloids (NiPx, NiSx, and NiSex) to in-situ construct different oxyanion-coordinated amorphous nickel oxyhydroxides (NiOOH-TOx), among which NiOOH-POx shows optimal local coordination environment and boosts electrocatalytic activity of Ni sites towards selective oxidation of methanol to formate. Experiments and theoretical results demonstrate that NiOOH-POx possesses improved adsorption of OH* and methanol, and favors the formation of CH3O* intermediates. The coordinated phosphate oxyanions effectively tailor the d band center of Ni sites and increases Ni-O covalency, promoting the catalytic activity. This study provides additional insights into modulation of active-center coordination environment via oxyanions for organic molecules transformation. Coordination environments around metal sites are important in electrocatalysis. Here, Ni metalloid oxidation produces oxyanion doped amorphous Ni-oxyhydroxides where substitution with phosphorus is found to boost methanol electrooxidation activity.
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影响因子：
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通讯作者：
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