Brookite TiO2 quasi nanocubes decorated with Cu nanoclusters for enhanced photocatalytic hydrogen production activity

One‐Pot Synthesis of Cu‐Nanocluster‐Decorated Brookite TiO2Quasi‐Nanocubes for Enhanced Activity and Selectivity of CO2 Photoreduction to CH4

“…After the decoration of Cu nanoclusters,v isible absorptions with at ailing at 400-500 and ar elatively strong peak at % 800 nm are observed.I tw as reported that surface plasmon resonanceo fm etallic Cu is in the range of 400-600nm, and the formation of surfaceC uo xide will show up as an absorption peak in l > 600 nm region. [34,42] These visible absorptions of Cu-BTN show an increasing trend with increasing Cu-loading contents, indicating it is really causedb yt he contribution of O-Cu species possibly formed at the interface of BTN and Cu nanoclusters. [42] Therefore, it can be concluded that the VB of Cu-BTN can be risen, and then causest he band gap getting narrowed partly.…”

“…CO/CH 4 production rates (a) and the corresponding total consumed electron numbers( TCEN) (b) for the CO 2 photoreduction over pristine BTN andCu-BTN productionw ith different Cu loading contentsd uring the initial 2hof irradiation. ChemPhysChem 2017, 18,3230 -3239 www.chemphyschem.org exhibits the best overall photoactivity( TCEN = 40.8 mmol g À1 h À1 ), much lower than that (TCEN = 150.9 mmol g À1 h À1 )o fthe present1 .5 %C u-BTN, even though 0.5 %C u/BTN has an actual Cu-loading content (0.45 mol % [34] ) very closet ot hat (0.42 mol %) of 1.5 %C u-BTN (Table S2). Also, the post-deposited Cu/BTN products exhibit more obviously selectiveC Og eneration as compared to CH 4 ( Figure S2), which is similar to the pristineB TN but opposite to the Cu-BTN products (Figure 7).…”

“…[41] For comparison, metallicC un anoclusters with smalls ize of 1-2 nm were post-deposited on the BTN surfaces via aN aBH 4 chemical reduction process according to the previousr eports. [29,34] Those post-deposited Cu-loaded BTN products (referred as Cu/BTN forc onvenience) are adopted as photocatalyst under the same CO 2 photoreduction conditions. As shown in Figure S2, af irst increasing and then decreasing trend in the overall photoactivity (TCEN) can also be observed after the post-loading of Cu nanoclusters on BTN surfaces, which is similar to the Figure 7b.A mong which, 0.5 %C u/BTN Figure 7.…”

“…[20] Compared to noble metals (such as Pt, Ag, Rh), transition metal/metal oxides are more attractive co-catalysts for lowcost photocatalytic applications. [32][33][34][35][36][37][38][39][40][41][42][43] In particular,v arious Cu speciess uch as Cu [32,38] and CuO x [39,40] have been used to promote the photoactivity of anatase TiO 2 due to its advantages such as abundance,n on-toxicity,a nd large work function (4.65 eV). [34][35][36][37][38] Herein, Cu nanoclusters decorated brookite TiO 2 quasi nanocubes (BTN) surfaces (Cu-BTN) are synthesized via a one-pot hydrothermal process and applieda sp hotocatalyst for CO 2 photoreduction with H 2 Ot og enerate solar fuels.…”

“…The effects of Cu nanoclusters decoration on the crystal structure, morphology,o ptical absorption, surface state, CO 2 photoreduction activity and selectivityo ft he BTN were investigated. For comparison, Cu nanoclusters wasa lso post-depositedo nt he BTN surface via aN aBH 4 chemical reduction process according to our previous report, [34] and the corresponding product is referred as Cu/BTN. Although the two Cu-loaded BTN products have similar Cu species, particles ize, dispersity and loading content on BTN surfaces, the one-pot decorated Cu-BTN product shows significantly enhanced photoactivity and selectivity for CO 2 reduction to CH 4 as compared to the pristine BTN and the post-deposited Cu/BTN.…”