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在现代化学合成的精密世界里,过渡金属(如钯、铂、铑)一直发挥着重要作用。它们如同身怀绝技的“分子工匠”,能高效地搭建起从治病良药到高科技材料的各类复杂分子。2010年,诺贝尔化学奖授予了在“钯催化交叉偶联反应”领域做出杰出贡献的3位科学家,足见这项技术对人类生活的深刻影响。然而,这份依赖正变得昂贵而脆弱。

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(图片来源:维基百科)

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马星星 1 , 宋秋玲 2
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准金属催化能否减少贵金属依赖
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马星星1, 宋秋玲2
作者信息
  • 1福州大学化学学院,有机合成与功能福建省高校重点实验室,副教授
  • 2福州大学化学学院,教授
马星星1, 宋秋玲2
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出版时间: 2026-09-13
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在现代化学合成的精密世界里,过渡金属(如钯、铂、铑)一直发挥着重要作用。它们如同身怀绝技的“分子工匠”,能高效地搭建起从治病良药到高科技材料的各类复杂分子。2010年,诺贝尔化学奖授予了在“钯催化交叉偶联反应”领域做出杰出贡献的3位科学家,足见这项技术对人类生活的深刻影响。然而,这份依赖正变得昂贵而脆弱。

马星星, 宋秋玲. 准金属催化能否减少贵金属依赖. 科技导报, 2026 , 44 (17) : 14 -16 .
马星星, 宋秋玲. Science & Technology Review, 2026 , 44 (17) : 14 -16 .
在现代化学合成的精密世界里,过渡金属(如钯、铂、铑)一直发挥着重要作用。它们如同身怀绝技的“分子工匠”,能高效地搭建起从治病良药到高科技材料的各类复杂分子。2010年,诺贝尔化学奖授予了在“钯催化交叉偶联反应”领域做出杰出贡献的3位科学家,足见这项技术对人类生活的深刻影响。然而,这份依赖正变得昂贵而脆弱。
2024年,南非约占全球铂矿山产量的70%,这种地理上的高度集中意味着贸易摩擦或地缘冲突都可能直接冲击关键催化材料的稳定供应。与此同时,贵金属的开采与提纯伴随着高昂的环境代价。正是在多重压力叠加之下,合成化学家开始追问一个根本问题:能否用一类更普遍、更廉价、更绿色的元素——其地壳储量是铂系贵金属的数千甚至数万倍——去取代使用了数十年的传统“贵族”工具?
2025年7月,中国化学会推荐的“准金属替代过渡金属用于精准合成与催化反应的可行性研究”成功入选中国科协“十大前沿科学问题”。与“流形的拓扑和几何分类”“希格斯粒子性质和质量起源”等基础科学命题并肩而立,这一方向的战略意义已超越学术范畴——它关乎国家科技竞争力与未来产业自主能力。
在回答这个问题之前,我们首先要认识这位被长期忽视的“挑战者”。
在元素周期表的金属与非金属阵营之间,存在一个独特的“跨界”家族——准金属(又称类金属)。硼(B)、硅(Si)、锗(Ge)、砷(As)、锑(Sb)、碲(Te)等通常被认为是这个家族的核心成员。它们的位置“跨界”,性质也充满矛盾与统一:典型的准金属单质拥有金属般的光泽,质地却通常较脆;它们像金属一样具有一定的导电能力,却又不是顶尖的导体。这种独特的半导体特性,使其成为现代电子工业的基石——硅是芯片和玻璃的核心材料,硼可用于生产耐热玻璃。
与储量稀少、价格高昂的铂系贵金属相比,大多数准金属不仅在地壳中储量丰富,而且成本低廉。硅占地壳质量超过27%;硼、锗、锑等同样储量可观。正是这种独特且可调控的“双重性格”,让科学家们开始思考:能否请这位“跨界选手”接手那些虽高效却娇贵的“贵族”工匠的工作?
要理解这场变革的意义,首先需要明白过渡金属催化为何强大。
过渡金属(如钯、铂、铑)凭借其独特的d轨道电子结构,能在催化循环中灵活改变氧化态,通过氧化加成、还原消除等基元步骤,将惰性底物活化并连接在一起,自身在任务完成后恢复原状。
但这份依赖正变得不可持续:部分贵金属的生产高度集中,供应链存在风险;开采和精炼1kg钯排放约3880 kgCO2,环境代价高昂;昂贵的成本更使许多有潜力的化学工艺难以规模化落地。能否用准金属替代过渡金属?这一问题触及催化科学的核心——准金属以np价轨道为主,缺少过渡金属灵活变价的能力,不能照搬金属催化机理,而需发展专属于主族中心的活化模式。但这恰恰也是机遇所在。
准金属催化不只是替换金属中心,更可能催生全新的键活化模式——前者是工程问题,后者是科学革命。
近年来,准金属替代贵金属催化的研究已从概念验证走向具体突破。以下2个方向尤为值得关注。
1)硼:轻主族元素的催化潜力被逐步发掘。
以硼基化合物为骨架的“受阻路易斯酸碱对”(FLPs)化学,在氢化、硼氢化等反应中取得了积极进展。这类体系通过一种不涉及金属中心氧化态变化的机制,完成了一些传统上依赖贵金属才能实现的转化。
中国科学技术大学汪义丰、傅尧和张凤莲联合研究团队设计了一类手性氮环杂卡宾-硼自由基催化剂,发展了一种反应机制与催化循环均为全新的不对称环异构化反应(图 1)。手性硼自由基通过对炔烃的选择性加成、氢原子转移、分子内环化和消除4个基元步骤,完成了催化循环。这一策略规避了传统过渡金属催化的手性诱导困境,为轻主族元素不对称催化开辟了新路径。
2)锗与锡:重元素变价催化的技术突围。
相比轻主族元素,第14族重元素——尤其是具有准金属身份的锗(Ge)和邻近的锡(Sn)——的发展长期滞后。这类元素虽理论上具备多个可调氧化态,但由于配体设计策略不足,可靠实验证据迟迟未能出现。这一瓶颈近期被四川大学董召文课题组打破。
该团队创新设计了大立体位阻的三齿碳二膦烷钳形配体,用以稳定二价锗中心(图 2)。研究发现,该二价锗配合物能够以高底物普适性催化偶氮芳烃及亚胺的转移氢化反应。尤为重要的是,机理研究表明锗中心存在2条竞争性催化路径:一条为基于Ge(Ⅱ)/Ge(Ⅲ)/Ge(Ⅳ)氧化态循环的单电子转移过程,另一条为Ge(Ⅱ)/Ge(Ⅳ)直接互变的双电子转移机制。这是第14族重元素变价催化在单电子路径上的本质性突破。
尽管态势令人期待,但真正兼具高效催化转化性能、高选择性且路径清晰可控的准金属催化案例仍然有限。平心而论,上述挑战并非不可逾越的绝壁,而是任何新兴催化范式在走向成熟之前必经的试炼。
过渡金属催化在20世纪60~70年代同样经历过机理不明、配体匮乏的漫长摸索期。根本限制在于电子结构差异。主族元素以np价轨道为主,缺少过渡金属灵活切换氧化态的能力。对于Ge、Sn等多价态体系,虽然Ge(Ⅱ)/Ge(Ⅳ)之间的双电子氧化还原转化已初步实现,但其氧化还原能垒仍显著高于成熟的钯催化体系。
配体设计严重滞后。过渡金属催化的成功很大程度上依赖于丰富的手性配体库。而对于准金属催化,目前尚缺乏广泛适用的商品化配体库。
理论体系亟待建立。目前一线催化研究者选催化剂时,仍以过渡金属为主。准金属的引入从根本上挑战了这一成熟但高度依赖习惯的范式。全球科学界已认识到,将过渡金属催化模板不加批判地应用于所有场景的路径,正不可避免地撞上贵金属稀缺与地缘政治风险这两块坚石。
从实验室走向工业应用,准金属催化面临的根本挑战不在实验台,而在数十年来围绕过渡金属建立的思维定式。当前零星突破难以形成系统合力,亟需多学科协同攻关与人才培养体系的同步革新——教材和课程若仍将主族元素催化置于边缘,便很难催生真正颠覆性的认知跃迁。
但这场变革的终极目标,并非用准金属“平替”钯或铂,而是“跨越”:利用准金属独特的电子结构与反应模式,催生全然不同的键活化机制,去实现现有方法无法企及的精准合成。这既是一场催化剂迭代,更是一次对化学底层逻辑的重写,其一旦成真,将从创新药研发到新能源材料深刻重塑整个工业生态。
这条路或许需要10年甚至更久的求索,但对于正从化学大国迈向化学强国的中国而言,这既是科学前沿的挑战,也是掌握未来产业自主权的历史机遇。全球科学家正站在重塑合成化学思维的同一起跑线上,而中国催化研究共同体,完全有机会走在这段征途的中央。
(科技新闻栏目编辑  黄文光)

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2026年第44卷第17期
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  • 首发时间:2026-10-14
  • 出版时间:2026-09-13
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    1福州大学化学学院,有机合成与功能福建省高校重点实验室,副教授
    2福州大学化学学院,教授
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2种不同金属材料的力学参数
科
Family
属数
Number of
genus
种数
Number of
species
占总种数比例
Percentage of
total species (%)
属
Genus
种数
Number of
species
占总种数比例
Percentage of total
species (%)
鹅膏菌科Amanitaceae 2 11 5.26 鹅膏菌属 Amanita 10 4.78
小菇科 Mycenaceae 2 12 5.74 丝盖伞属 Inocybe 5 2.39
多孔菌科 Polyporaceae 8 14 6.70 蜡蘑属 Laccaria 5 2.39
红菇科 Russulaceae 3 23 11.00 小皮伞属 Marasmius 6 2.87
小菇属 Mycena 11 5.26
光柄菇属 Pluteus 5 2.39
红菇属 Russula 17 8.13
栓菌属 Trametes 5 2.39
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