Nanostructuring unlocks high performance of platinum single-atom catalysts for stable vinyl chloride production

Kaiser, Selina K.; Fako, Edvin; Manzocchi, Gabriele; Krumeich, Frank; Hauert, Roland; Clark, Adam H.; Safonova, Оlga V.; López, Núria; Pérez‐Ramírez, Javier

doi:10.1038/s41929-020-0431-3

Cited by 159 publications

(196 citation statements)

References 55 publications

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“…Variation of the speciation of metal atoms on carbon supports enabled the development of the first stable heterogeneous catalyst for the sustainable production of vinyl chloride via acetylene hydrochlorination (Fig. 1, L15) 8 . Whereas initial attempts focused on gold single atoms supported on nitrogen-doped carbons due to their superior activity, the presence of the heteroatom in the support led to rapid deactivation due to the deposition of carbonaceous deposits.…”

Section: Tailored Local Environmentsmentioning

confidence: 99%

Single atom catalysis: a decade of stunning progress and the promise for a bright future

2020

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Controlling the hybridization of single atoms in suitable host materials opens unique opportunities for catalyst design, but equally faces many challenges. Here, we highlight emerging directions from the last, highly productive, decade in single-atom catalysis and identify frontiers for future research. Origins and evolution of single-atom catalysis The isolation of elements as atoms in chemically-distinct substances played fundamental catalytic roles, for example, in metalloenzymes, organometallic complexes, and open framework structures, long before this concept was extended to widely applied heterogeneous catalysts based on supported metals. In pioneering early work, Flytzani-Stephanopoulos et al. provided convincing evidence that ionic gold or platinum species strongly associated with the surface of ceria, and not the metal nanoparticles, were responsible for the activity observed in the water-gas shift reaction (Fig. 1, L1) 1. Subsequently, Bashyam and Zelenay proposed that oxidized cobalt and iron species coordinated to nitrogen and oxygen in functionalized carbons deliver high performance in the electrochemical oxygen reduction reaction (Fig. 1, L2) 2. After years of speculation about the catalytic role of single atoms of this group of elements, advances in experimental techniques made it possible to confirm the exclusive presence of isolated centers. In their landmark paper, Zhang et al. confirmed the high efficiency of platinum atoms supported on iron oxide for CO oxidation, introducing a new paradigm in heterogeneous catalysis (Fig. 1, L3) 3. The first catalytic applications of single-atom alloys based on metal hosts followed shortly after (Fig. 1, L5) 4. In just a decade, the topic of single-atom catalysis has become a highly transversal field of contemporary chemical research. Early researchers quickly recognized the potential cost benefits of using atomically-dispersed species for precious metals, and improving the utilization became a central driver in the topic. As the area developed, the motivation also evolved. Comparative studies revealed that the strategy of using SACs does not apply to all applications and depends on the reaction requirements 5. Another strength is the higher uniformity of potential active sites in heterogeneous catalysts based on single atoms compared to nanoparticles. The well-defined nature is attractive for both defining structure-function relationships and computational modeling. Furthermore, the close structural resemblance to molecular complexes provides a bridge between homogeneous and heterogeneous catalysis. On the 10-year journey since the consolidation of the topic, single-atom catalysis has crossed the periodic table. The diversity of host materials has also expanded. While metal oxides were initially most widely studied, tailored carbons have superseded all other types in the last years.

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Section: Tailored Local Environmentsmentioning

confidence: 99%

Single atom catalysis: a decade of stunning progress and the promise for a bright future

2020

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“…Single-atom catalysts (SACs), with atomically distributed metal centers and maximized atom utilization efficiency, have attracted great attention in catalysis owing to the integrated merits of homogeneous and heterogeneous catalysts (12)(13)(14)(15)(16)(17). The distinct atomic microenvironment (defined as a small, specific, and isolated chemicophysical environment, such as the local coordination environment and electronic state of the catalytic center) of SACs offers remarkable advantages to achieve high activity, selectivity, and stability for heterogeneous catalysis (18)(19)(20)(21)(22) and electrochemical applications (23)(24)(25)(26)(27)(28). Previously, we have thoroughly summarized the advances of supported noble metal SACs for heterogeneous catalysis (15); however, few reports specified and highlighted the microenvironment engineering of SACs for electrochemical applications.…”

Section: Introductionmentioning

confidence: 99%

Microenvironment modulation of single-atom catalysts and their roles in electrochemical energy conversion

et al. 2020

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Single-atom catalysts (SACs) have become the most attractive frontier research field in heterogeneous catalysis. Since the atomically dispersed metal atoms are commonly stabilized by ionic/covalent interactions with neighboring atoms, the geometric and electronic structures of SACs depend greatly on their microenvironment, which, in turn, determine the performances in catalytic processes. In this review, we will focus on the recently developed strategies of SAC synthesis, with attention on the microenvironment modulation of single-atom active sites of SACs. Furthermore, experimental and computational advances in understanding such microenvironment in association to the catalytic activity and mechanisms are summarized and exemplified in the electrochemical applications, including the water electrolysis and O2/CO2/N2 reduction reactions. Last, by highlighting the prospects and challenges for microenvironment engineering of SACs, we wish to shed some light on the further development of SACs for electrochemical energy conversion.

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“…Downsizing metal nanocatalysts to the sub-nanometric ones (cluster and single atom) has been a powerful yet challenging strategy to break the limits of traditional catalysts for superior catalytic performance in addition to ultra-high atom utilization. [1][2][3][4][5][6][7] For such unique complex sub-nanostructure bonding with the support, a change of even only one atom usually brings signi cant electronic and geometric properties compared to traditional nanocatalysts. [6][7][8][9][10][11] This calls for more fundamental understanding, because classical catalytic theories are not entirely applicable to sub-nanocatalysis.…”

Section: Introductionmentioning

confidence: 99%

Atomic Design and Fine-Tuning of Subnanometric Pt Catalysts to Tame Hydrogen Generation

Yang

Chen

et al. 2021

ACS Catal.

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Rational synthesis of sub-nanocatalysts with controllable electronic and atomic structures remains a challenge to break the limits of traditional catalysts for superior performance. Here we report the atomiclevel precise synthesis of Pt/graphene sub-nanocatalysts (from single atom, dimer, and to cluster) by atomic layer deposition, achieved by a novel high temperature pulsed ozone strategy to controllably precreate abundant in-plane epoxy groups on graphene as anchoring sites. The speci c in-plane epoxy structure endows the deposited Pt species with outstanding uniformity, controllability and stability. Their size-depended electronic and geometric effects have been observed for ammonia borane hydrolysis, revealing a volcano-type dependence of intrinsic activity on their sizes. Their active site structures have been identi ed based on extensive characterizations, dynamic compensation effect, kinetic isotope experiments and density function theory simulation. The Pt dimers show the highest catalytic activity and good durability than Pt single atoms and nanoparticles, ascribed to the unique C-Pt-Pt-O (C5Pt2O, metalmetal bond dimer) active site structure. Our work provides new insights into the precise tailoring and catalytic mechanism in sub-nanometer level.

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Nanostructuring unlocks high performance of platinum single-atom catalysts for stable vinyl chloride production

Abstract: Pérez-Ramírez, J. (2020). Nanostructuring unlocks high performance of platinum singleatom catalysts for stable vinyl chloride production. Nature Catalysis, 3(4), 376-385.

Cited by 159 publications

References 55 publications

Single atom catalysis: a decade of stunning progress and the promise for a bright future

Single atom catalysis: a decade of stunning progress and the promise for a bright future

Microenvironment modulation of single-atom catalysts and their roles in electrochemical energy conversion

Atomic Design and Fine-Tuning of Subnanometric Pt Catalysts to Tame Hydrogen Generation

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