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A promising method of catalyst synthesis is atomic layer deposition (ALD). ALD is a variation on chemical vapor deposition in which metals, oxides, and other materials are deposited on surfaces by a sequence of self-limiting reactions. The self-limiting character of these reactions makes it possible to achieve uniform deposits on high-surface-area porous solids. Therefore, design and synthesis of advanced catalysts on the nanoscale becomes possible through precise control over the structure and composition of the underlying support, the catalytic active sites, and the protective layer. In this Account, we describe our advances in the synthesis and stabilization of supported metal catalysts by ALD. After a short introduction to the technique of ALD, we show several strategies for metal catalyst synthesis by ALD that take advantage of its self-limiting feature. Monometallic and bimetallic catalysts with precise control over the metal particle size, composition, and structure were achieved by combining ALD sequences, surface treatments, and deposition temperature control. Next, we describe ALD oxide overcoats applied with atomically precise thickness control that stabilize metal catalysts while preserving their catalytic function. We also discuss strategies for generation and control over the porosity of the overcoats that allow the embedded metal particles to remain accessible by reactants, and the details for ALD alumina overcoats on metal catalysts. Moreover, using methanol decomposition and oxidative dehydrogenation of ethane as probe reactions, we demonstrate that selectively blocking low coordination metal sites by oxide overcoats can provide another strategy to enhance both the durability and selectivity of metal catalysts. ¸ºÔØÐͽðÊô´ß»¯¼ÁÔÚºÜ¶à·½ÃæÓÐ×ŷdz£ÖØÒªµÄÓ¦Óã¬È磺ʯÓÍ»¯¹¤¡¢Æû³µÎ²Æø´¦ÀíºÍ·ÑÍкϳɡ£½ðÊôÄÉÃ׿ÅÁ£µÄÁ£¾¶¡¢×é³ÉºÍ½á¹¹¶¼»á¶ÔÆä´ß»¯ÐÔÖÊÔì³ÉÓ°Ïì¡£µ«ÊÇÒ»¸ö·Ç³£ÑϾþµÄÎÊÌâ¾ÍÊǽðÊôÄÉÃ׿ÅÁ£ÔÚ¸ßÎÂÏÂÒ×ÉÕ½á»òÕ߽ό£¨Ê¯ÓÍ»¯¹¤ÖУ©£¬ËùÒÔ±£»¤½ðÊôÄÉÃ׿ÅÁ£Ê¹ÆäÃâÓÚÉÕ½á»òÕ߽όÊÇÒ»¸ö·Ç³£ÆÈÇеÄÎÊÌ⡣ʵÑé±íÃ÷ÀûÓþۺÏÎï»òÕßÑõ»¯Îï²ã±£»¤½ðÊôÄÉÃ׿ÅÁ£ÊǸöºÜºÃµÄ°ì·¨£¬µ«ÊÇÈç¹û±£»¤²ãÌ«ºñ»áÑÏÖØ½µµÍ´ß»¯¼ÁµÄ»îÐÔ¡£ ÕâÆª×ÛÊö²ûÊöÁËÔ×Ó²ã³Á»ý£¨ALD£©·½·¨ÔÚ¸ºÔØÐÍ´ß»¯¼ÁÉϳÁ»ý±£»¤²ãµÄÓ¦Óã¬ALDÓëÆäËü·½·¨ÔÚÕâ¸ö·½Ãæ×î´óµÄÓÅÊÆ¾ÍÊÇÄܹ»¾«È·¿ØÖƱ£»¤²ãµÄºñ¶È£¬±£»¤²ãµÄºñ¶ÈÄܹ»ºÜÈÝÒ××öµ½1nm¡£ÁíÍ⣬ALDÒ²¿ÉÒÔÖÆ±¸Ë«½ðÊôÄÉÃ×´ß»¯¼Á¡£ÔÚÖÆ±¸Ë«½ðÊôÄÉÃ×´ß»¯¼ÁµÄʱºò»áÓпÅÁ£µÄÑ¡ÔñÐÔÉú³¤¡£ ÆäËüµÄ×Ô¼º¿´°É£¬×Ô¼º¿´Á˲ÅÖªµÀ¡£ |
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