TY - JOUR
T1 - Core-substituted naphthalenediimides anchored on BiVO4 for visible light-driven water splitting
AU - Hernández, Simelys
AU - Ottone, Carminna
AU - Proto, Stefano
AU - Tolod, Kristhine
AU - Díaz De Los Bernardos, Miriam
AU - Solé-Daura, Albert
AU - Carbó, Jorge J.
AU - Godard, Cyril
AU - Castillón, Sergio
AU - Russo, Nunzio
AU - Saracco, Guido
AU - Claver, Carmen
N1 - Funding Information:
Sitaramanjaneya Mouli Thalluri, Mauro Raimondo and Salvatore Guastella are acknowledged for the technical support during the synthesis of the BiVO4 powders, and FESEM and XPS measurements, respectively. This work has been funded by the EU Commission, 7th European Framework Program (NMP-2012), Project Eco2CO2, Grant Agreement number 309701. Computational research was supported by the Spanish Ministry of Science and Innovation (CTQ2014-52774-P) and the Generalitat de Catalunya (2014SGR199 and XRQTC). The CTQC/URV authors acknowledge the Spanish Ministerio de Econom?a y Competitividad (CTQ2013-43438-R) and the Generalitat de Catalunya (2014SGR670) for financial support.
Publisher Copyright:
© The Royal Society of Chemistry 2017.
PY - 2017
Y1 - 2017
N2 - In this work, a novel catalytic system for the sunlight-driven water splitting reaction, which exploits the photocatalytic ability of BiVO4 coupled to a new kind of noble-metal-free organic dye molecules, is proposed. Hence, mono- and di-substituted naphthalenediimides (NDIs) were designed to have different functional groups that provide to them both tunable optical properties and adjustable HOMO/LUMO levels, and were selectively prepared (starting from 1,4,5,8-naphthalenetetracarboxylic acid) achieving yields >69%. Smart anchoring groups (i.e. carboxylates or aromatic amines) were added to the dyes in order to allow them to covalently bond to acidic -OH groups present on the BiVO4 surface. An easy and low-cost room temperature dip-coating technique was used to dye-sensitize both BiVO4 powders and thin films. NMR, MS, FT-IR, TG, FESEM, XRD, XPS and optical analyses confirmed the successful organic synthetic routes and good dyes/BiVO4 linkages. Photochemical and photoelectrochemical water oxidation reaction tests, together with DFT calculations, demonstrated that a proper alignment of the semiconductor/NDI-based dye energy levels is fundamental for enhancing the photocatalyst performance through a Z-scheme mechanism. The ability of the NDI organic molecules to delocalize the electronic charges was also a key factor for minimizing recombination processes and achieving more than a ten-fold increase in the photocurrent density of a 6 cm2 BiVO4 photo-electrode. The here reported results open new perspectives for the utilization of this new series of core-substituted NDIs, which are able to improve the activity of photocatalysts for different sunlight-driven applications, e.g. waste water treatment and organic contaminants' degradation, other than the production of solar fuels by water splitting mechanisms.
AB - In this work, a novel catalytic system for the sunlight-driven water splitting reaction, which exploits the photocatalytic ability of BiVO4 coupled to a new kind of noble-metal-free organic dye molecules, is proposed. Hence, mono- and di-substituted naphthalenediimides (NDIs) were designed to have different functional groups that provide to them both tunable optical properties and adjustable HOMO/LUMO levels, and were selectively prepared (starting from 1,4,5,8-naphthalenetetracarboxylic acid) achieving yields >69%. Smart anchoring groups (i.e. carboxylates or aromatic amines) were added to the dyes in order to allow them to covalently bond to acidic -OH groups present on the BiVO4 surface. An easy and low-cost room temperature dip-coating technique was used to dye-sensitize both BiVO4 powders and thin films. NMR, MS, FT-IR, TG, FESEM, XRD, XPS and optical analyses confirmed the successful organic synthetic routes and good dyes/BiVO4 linkages. Photochemical and photoelectrochemical water oxidation reaction tests, together with DFT calculations, demonstrated that a proper alignment of the semiconductor/NDI-based dye energy levels is fundamental for enhancing the photocatalyst performance through a Z-scheme mechanism. The ability of the NDI organic molecules to delocalize the electronic charges was also a key factor for minimizing recombination processes and achieving more than a ten-fold increase in the photocurrent density of a 6 cm2 BiVO4 photo-electrode. The here reported results open new perspectives for the utilization of this new series of core-substituted NDIs, which are able to improve the activity of photocatalysts for different sunlight-driven applications, e.g. waste water treatment and organic contaminants' degradation, other than the production of solar fuels by water splitting mechanisms.
UR - http://www.scopus.com/inward/record.url?scp=85021969474&partnerID=8YFLogxK
U2 - 10.1039/c7gc00125h
DO - 10.1039/c7gc00125h
M3 - Article
AN - SCOPUS:85021969474
VL - 19
SP - 2448
EP - 2462
JO - Green Chemistry
JF - Green Chemistry
SN - 1463-9262
IS - 10
ER -