Solar RRL: Zhejiang University silicon materials Sun Wei, Yang Deren team review: photocatalytic two dimensional silicon materials

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two-dimensional silicon is a new kind of photocatalyst. It not only inherits the characteristics of high silicon abundance low toxicity strong light trapping ability but also has the general advantages of two-dimensional materials (large specific surface area rich active sites other element loading sites ultra-thin thickness is conducive to defect generation photo generated carrier transport etc.). In addition 2D silicon has unique surface chemistry metal carrier mechanism. These two-dimensional silicon photocatalysts are promising.

accordingly Sun Wei research group of State Key Laboratory of silicon materials of Zhejiang University (academician Yang Deren silicon materials research group) recently published the synthesis of two-dimensional silicon based photocatalytic structure various catalytic reaction applications in solar RRL.

in this paper two-dimensional silicon mainly refers to the saturated derivatives of silylene its SP3 hybrid silicon atoms (including hydroxyl or organic terminated silylene siloxane). It lays a foundation for the development of two-dimensional silicon synthesis technology. At present the main synthesis methods of two-dimensional silicon are epitaxial growth chemical stripping chemical vapor deposition (Fig. 1). Among these methods the chemical stripping method can achieve large-scale production there is still a large space to control the structure surface chemistry of two-dimensional silicon which is conducive to the application of two-dimensional silicon in the field of catalysis. [1]

figure 1: typical two-dimensional silicon preparation methods [1]: epitaxial growth (top left reproduced with permission. [2] copyright 2012 American Chemical Society.); chemical stripping (top right reproduced with permission. [3] copyright 2019 As a new type of photocatalyst

two-dimensional silicon has unique advantages. First of all its rich adjustable surface chemistry is very conducive to the adsorption dissociation of reactant molecules. There are three groups on the surface of two-dimensional silicon: Si-O-Si Si oh si-h. SiO2 is usually inert can be endowed with catalytic ability by introducing defects. The hydrophilic silicon hydroxyl group makes the two-dimensional silicon well dispersed in the aqueous solution so that it can fully contact with the reactants in the aqueous reaction. Active - OH groups can also be cross-linked with a variety of surfactants functional groups so that two-dimensional silicon can be grafted with a large number of useful ligs (such as - NH2 - SH) as needed. In addition the - OH group can promote water dissociation (an important step in water gas conversion steam reforming) reduce carbon deposition (the main cause of catalyst deactivation in high temperature carbon containing reactions). The reduced Si-H group can directly participate in the catalytic reaction. In addition Si-H group can also reduce some metal ions to metal state under mild conditions. Therefore si-h-capped two-dimensional silicon can be a good carrier reducing agent for the preparation of metal / two-dimensional silicon composites. In conclusion the three common groups on the surface of two-dimensional silicon play an important role in the catalytic reaction. Besides abundant surface chemistry the strong interaction between two-dimensional silicon metal the structural regulation of "metal / two-dimensional silicon" provide a new way to improve the stability of catalysts the selectivity of products. At present some preliminary progress has been made in photocatalytic reduction of carbon dioxide photolysis of water photocatalytic degradation of no which paves the way for its future development. Based on this we made some prospects for the future development of two-dimensional silicon in the field of catalysis:

1. Develop simpler more economical synthesis strategies batch synthesis of two-dimensional silicon with single or several atomic layers; 2 The reasonable regulation of b gap surface chemistry metal carrier interaction of two-dimensional silicon can make them excellent cidates for various photocatalytic reactions The highly active Si-H bonds on the surface of two-dimensional silicon deserve special attention because they can be used as reactants directly in chemical reactions or as reducing agents to support specific ionic metals under mild conditions. There are still numerous combinations of different active metals their alloys to be explored to adapt to different heterogeneous catalytic reactions; 4. Two dimensional silicon can be further exped to produce more kinds of fuels other valuable chemical raw materials; 5. In addition to removing toxic gases two dimensional silicon can also photodegradate organic pollutants (such as 4-nitrophenol methyl orange); 6 As another group IV element germanium has many similarities with silicon so it also has broad application prospects in the field of photocatalysis. [1]

believe that two-dimensional silicon can flourish like other two-dimensional materials gradually show its strength in photocatalytic reactions.

Fig. 2. (a) palladium supported silicon nanosheets（ Pd@SiNS ）[5] copyright 2019 Springer nature Pd@SiNS The catalytic cycle of carbon dioxide hydrogenation was carried out (c) two different structures were obtained by impregnating the samples with Ni2 in water ethanol respectively. The black spheres around the green sixns plate represent Ni2 (reproduced with permission. [6] copyright 2019 Springer nature.); (d) sigenes with different x values are used for carbon dioxide reduction to carbon monoxide hydrogen production (reproduced with permission. [7] copyright 2020 Springer nature.) [1]

References:

[1] s. h. Wang † C. H. Wang† W. B. Pan W. Sun* D. R. D. R. Yang*. Two-dimensional Silicon for (Photo)Catalysis. Solar RRL doi: 10.1002/solr.202000392

[2] B. J. Feng Z. J. Ding S. Meng Y. G. Yao X. Y. He P. Cheng L. Chen K. H. Wu Nano Lett. 2012 12 3507.

[3] P. Pazhamalai K. Krishnamoorthy S. Sahoo V. K. Mariappan S.-J. Kim ACS Appl. Mater. Interfaces 2019 11 624.

[4] S. Chen Z. Chen X. Xu C. Cao M. Xia Y. Luo Small 2018 14 11.

[5] C. X. Qian W. Sun D. L. H. Hung C. Y. Qiu M. Makaremi S. G. H. Kumar L. L. Wan M. Ghoussoub T. E. Wood M. K. Xia A. A. Tountas Y. F. Li L. Wang Y. C. Dong I. Gourevich C. V. Singh G. A. Ozin Nat. Catal. 2019 2 46.

[6] X. L. Yan W. Sun L. M. Fan P. N. Duchesne W. Wang C. Kubel D. Wang S. G. H. Kumar Y. F. Li A. Tavasoli T. E. Wood D. L. H. Hung L. L. Wan L. Wang R. Song J. L. Guo I. Gourevich A. A. Jelle J. J. Lu R. F. Li B. D. Hatton G. A. Ozin Nat. Commun. 2019 10 11.

[7] F. L. Zhao Y. Y. Feng Y. Wang X. Zhang X. J. Liang Z. Li F. Zhang T. Wang J. L. Gong W. Feng Nat. Commun. 2020 11 13."

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