Chemistry

Nanostructured bismuth vanadate/tungsten oxide photoanode for chlorine manufacturing with hydrogen era on the darkish cathode

Synthesis and characterization

Particulars of the fabrication of BiVO4/WO3 photoanodes are offered within the strategies part. Briefly, the BiVO4/WO3 nanostructured movies had been deposited on conductive fluorine-doped tin oxide (FTO) coated glass substrate utilizing a two-step course of. Step one is the fabrication of crystalline BiVO4 gentle absorber unit following beforehand reported strategies17, the place electrodeposited bismuth oxyiodide (BiOI) is used as a precursor to kind BiVO4. (Fig. 1a, c) exhibits a high view and cross-sectional scanning electron microscopy (SEM) pictures of the naked BiVO4 electrode. The SEM pictures displayed a nanoporous structure for BiVO4 with interconnected particles of roughly 90 nm in diameter. A nanoporous structure with minority provider diffusion lengths on the order of 100 nm (as decided by the particle diameter) has been proven to boost cost separation effectivity whereas offering a big contact floor space on the BiVO4/electrolyte interface17,18.

Fig. 1Fig. 1

Structural characterization of BiVO4 and BiVO4/WO3. Prime view scanning electron microscopy (SEM) pictures of a naked BiVO4 and b BiVO4 electrode coated with 20 nm thick WO3 (scale bar – 1 µm) with inset displaying excessive magnification SEM pictures (scale bar – 200 nm). Cross sectional SEM pictures of c naked BiVO4 and d BIVO4/WO3 (scale bar – 500 nm). Excessive decision transmission electron microscopy (HRTEM) pictures of e naked BiVO4 (scale bar – 5 nm) and f BIVO4/WO3 (scale bar – 10 nm) with inset displaying quick Fourier rework (FFT) sample. g Power dispersive x-ray spectroscopy (EDS) elemental mapping of the core shell BiVO4/WO3 (scale bar – 75 nm)

The WO3 layer (~20 nm thick) was subsequently electrodeposited on BiVO4 (Fig. 1b) utilizing a peroxytungstic acid answer20. It’s to be famous that the tungsten oxide deposition was carried in darkish at pH 2 beneath cathodic situations to forestall photooxidative corrosion of BiVO425,26,27. We didn’t observe any chemical and/or electrochemical corrosion of the BiVO4 for the deposition durations investigated on this research. Remarkably, a conformal deposition of WO3 on the BiVO4 electrode was noticed right down to the bottom of the particle whereas preserving the nanoporous structure for environment friendly provider extraction (Fig. 1d). The thickness of the WO3 layers was tuned by adjusting the cost handed throughout electrodeposition (Supplementary Fig. 1). The optimum thickness was probed by evaluating their photoelectrochemical habits (Supplementary Fig. 2). Beneath the optimized situation, passing 100 mC cm−2 of cost at −zero.5V vs. silver/silver chloride (Ag/AgCl) electrode yielded WO3 thickness of ~20 nm. As proven later, a 20 nm thick WO3 movie was ample to stabilize BiVO4 in acidic pH situations whereas transmitting a lot of the incident gentle to BiVO4 (Supplementary Fig. three). Thicker movies weren’t discovered to extend pattern stability with the one observable impact being a lower in limiting present density possible because of parasitic gentle absorption or provider recombination by means of the WO3 movie. The general thickness of the BiVO4/WO3 movies as measured by the cross-sectional SEM pictures was about 600 nm (Fig. 1c, d). This thickness was chosen primarily based on prior studies which confirmed enhanced gentle absorption for 600 nm thick BiVO4 nanostructures with minimal cost recombination losses16.

The nanostructured BiVO4/WO3 movies had been additional characterised utilizing excessive decision transmission electron microscopy (HRTEM), energy-dispersive x-ray spectroscopy (EDS) and x-ray photoelectron spectroscopy (XPS). (Fig. 1e, f) exhibits HRTEM pictures and quick Fourier rework (FFT) patterns (Fig. 1e, f, inset) of each naked BiVO4 particle and BiVO4 coated with WO3. Low-magnification pictures are offered within the supplementary info (Supplementary Fig. four). The HRTEM picture revealed a crystalline construction for naked BiVO4 (Fig. 1e) with a lattice spacing of zero.307 nm, comparable to the (112) planes of BiVO4 (JCPDS file no. 14-0688). HRTEM pictures of the coated samples (Fig. 1f) confirmed a transparent interface between the BiVO4 core and WO3 shell with WO3 movie coated alongside the floor of the BiVO4 particle with a uniform thickness of 20 nm. The FFT sample indicated that the deposited WO3 movie was amorphous in nature (Fig. 1f, inset). EDS elemental mapping (Fig. 1g) revealed the compositional variation of the BiVO4/WO3 particle. The W sign was recorded from your entire space, supporting the conformal coating geometry. Robust Bi and V alerts had been obtained from the middle area additional indicating the existence of the core–shell structure of the BiVO4/WO3 particle. No W sign was detected from the naked BiVO4 movies (Supplementary Fig. 5). The chemical nature of the BiVO4/WO3 electrode was investigated utilizing XPS (Supplementary Fig. 6). The attribute Bi 4f and V 2p peaks had been recognized within the survey spectra of the naked BiVO4 pattern. For the tungsten coated particles symmetric W 4f peaks had been recognized at 37.7 eV and 35.6 eV indicative of the trioxide species (Supplementary Fig. 7)24.

PEC characterization

The PEC properties of the BiVO4/WO3 photoanodes had been characterised in a three-electrode configuration with BiVO4/WO3 as working electrode, and Ag/AgCl reference electrode and Pt as counter electrode separated utilizing a glass frit. Photoelectrooxidation of chloride ions utilizing BiVO4/WO3 photoanode meeting could be defined conceptually by referring to (Fig. 2a, b). Upon illumination, photogenerated holes in BiVO4 are carried away to the floor by means of amorphous WO3 movies the place it oxidizes chloride ions to chlorine (Fig. 2b). The electrons offered from the oxidation step are transferred by means of an exterior circuit to a darkish Pt cathode for hydrogen manufacturing.

Fig. 2Fig. 2

Photoelectrochemical efficiency of BiVO4 and BiVO4/WO3. a Schematic displaying the general response scheme and b cost switch course of on the photoanode. Present density – potential (VRHE) plots of BiVO4 and BiVO4/WO3 coated samples in c sodium sulfite gap scavenger answer and d in four M NaCl pH 1 answer

To substantiate that the amorphous WO3 layer doesn’t intervene with the photogenerated provider transport properties of underlying BiVO4 movies, the PEC efficiency of BiVO4/WO3 photoanode was first investigated in a phosphate buffer answer containing sodium sulfite as a gap scavenger. Prior research have proven that sulfite oxidation is kinetically and thermodynamically favorable on BiVO4 electrodes and can be utilized as a benchmark electrolyte to decouple cost separation effectivity from kinetic losses16,17,18. Determine 2c exhibits the everyday photocurrent densities obtained for sulfite oxidation as a operate of the utilized potential beneath 1 solar illumination (AM 1.5G; 100 mWcm−2). All potentials are referenced to reversible hydrogen electrode [VRHE; VRHE = VAg/AgCl + 0.197 V + 0.059 pH] and all PEC outcomes proven listed below are common values obtained from three samples. A median photocurrent density of three mA cm−2 was achieved for BiVO4/WO3 movies at 1.2 VRHE. Photocurrent densities of BiVO4/WO3 had been inside ±zero.1mAcm−2 (±three%) in comparison with the naked BiVO4 electrode floor (Fig. 2c, inexperienced hint) indicating that the amorphous WO3 ready through electrodeposition method features effectively as a gap transport layer with minimal resistive losses.

The PEC efficiency of BiVO4/WO3 movies for chloride oxidation was characterised in four M NaCl answer with pH adjusted to 1 utilizing HCl. Determine 2nd exhibits photocurrent density–potential plots for naked BiVO4 and BiVO4/WO3 photoanodes after 10 sweeps. All plots are common of three completely different samples and the depicted information are from the 10th linear sweep voltammetric cycle (Fig. 2nd). All 10 sweeps for a given BiVO4 and BiVO4/WO3 pattern could be present in Supplementary Fig. eight. Every cycle was scanned at a fee of 20 mVs−1, adopted by a relaxation interval of 30 s. Within the absence of sunshine, negligible anodic present densities (i < 10μAcm−2) had been noticed for naked BiVO4 and BiVO4/WO3 samples (Fig. 2nd, dashed traces). Upon illumination, the BiVO4/WO3 photoanode meeting confirmed a limiting photocurrent density of two.eight mAcm−2 at 1.6VRHE. The limiting photocurrent densities obtained had been solely barely decrease (≤zero.2 mAcm−2) than these noticed for a similar electrodes in touch with the sulfite answer indicating that the chloride oxidation may very well be carried out effectively utilizing holes transported to the floor of amorphous WO3 layer with out the necessity for a further catalyst.

We additionally carried out incident photon to present effectivity (IPCE) measurements of the WO3 coated samples at 1.42 VRHE (Supplementary Fig. 9). Integrating the IPCE values yielded a photocurrent density of two.61 mA cm−2 which is inside 5% of the measured photocurrent obtained beneath simulated daylight experiments (Fig. 2nd, magenta hint). The onset potential – outlined because the potential at which anodic photocurrent density reaches 20 µAcm−2 – was zero.67 VRHE for the BiVO4/WO3 pattern. This resulted in an estimated photovoltage of zero.75 V after subtracting the thermodynamic potential requirement for chlorine manufacturing (1.42 VRHE). For the naked BiVO4 pattern, the photocurrents decreased with cycle quantity with the 10th cycle displaying a most photocurrent density of zero.75 mAcm−2 at1.6 VRHE. The as deposited WO3 movie themselves had been discovered to have negligible photoactivity which helps their major position in facilitating cost transport versus electron gap pair era (Supplementary Fig. 10).

Stability and product evaluation

The sturdiness of the photoanodes for chloride oxidation was assessed by measuring the photocurrent density as a operate of time at a continuing exterior bias of 1.42 VRHE (Fig. 3a). Naked BiVO4 demonstrated increased preliminary photocurrents in comparison with WO3 coated samples nevertheless the present quickly declined over the primary jiffy indicating the excessive exercise is as a result of fast photo-corrosion course of as seen by the whole disappearance of the movie after 15 min (Supplementary Fig. 11). Prior research have proven that BiVO4 when operated in chloride electrolytes beneath pH three oxidizes to BiOCl with the dissolution of vanadium leading to materials degradation25,26,27,28. Quite the opposite, BiVO4 samples with WO3 layer as skinny as 20 nm exhibited enhanced stability sustaining >95% of preliminary photocurrent density after three h of steady illumination (the period of those stability assessments).

Fig. threeFig. 3

Photoelectrochemical (PEC) stability of BiVO4 and BiVO4/WO3. a Photocurrent density – time transient plot for BiVO4 and BiVO4/WO3 pattern for chloride oxidation at 1.42 VRHE beneath 1 solar illumination. b Power dispersive x-ray spectroscopy (EDS) elemental mapping of the BiVO4/WO3 construction put up operation with its corresponding transmission electron microscopy picture (150 nm scale bar). c Core degree x-ray photoelectron spectroscopy (XPS) scans of W, Bi, and V as ready (pink hint) and after PEC operation (blue hint). Core degree scans of W, Bi, and V after removing of WO3 layer put up operation can also be proven (brown hint)

Evaluation of the BiVO4/WO3 electrodes put up PEC operation by HRTEM-EDS revealed that the BiVO4 core layer was intact after PEC operation with W sign current all through and extra pronounced on the fringe of the particles (Fig. 3b). Moreover, no change in chemical atmosphere of the WO3 layer was noticed put up operation through XPS (Fig. 3c). To acquire chemical info of the underlying BiVO4 layer post-operation, the WO3 layer after PEC operation was eliminated by soaking it in sodium hydroxide answer for 15 min. Inside this time-frame, the NaOH solely etches WO3 layer with out affecting the underlying BiVO4. Core degree XPS scans of the Bi 4f and V 2p scans confirmed peaks equivalent to that of the naked BiVO4 electrode (Fig. 3c). The above outcomes unequivocally display that the electrodeposited amorphous WO3 layer might probably provide a easy and scalable route to guard the underlying nanostructured BiVO4 when operated in acidic media, whereas nonetheless permitting for environment friendly transport of holes between the answer and the BiVO4 electrode. Though WO3 coated BIVO4 samples stay visibly intact for longer period stability runs (~12 h), a linear lower in photocurrent (~10% normalized photocurrent h−1) was noticed after three hours. We attribute this drop-in efficiency on account of deactivation of WO3 on account of accumulation of peroxo species on the floor as reported beforehand22,29,30.

After 2 h of fixed potential (1.42 VRHE) PEC runs, the collected merchandise had been analyzed to find out the faradaic effectivity of the method (Fig. four). H2 and O2 had been investigated utilizing fuel chromatography. Chlorine was swept from the electrolyte answer by a sluggish helium (He) purge right into a potassium iodide answer, and the quantity of dissolved chlorine was then measured by Iodometric titration31. Previous to the soundness assessments, the system was purged with a pure He stream for 2 hours. Close to unity faradaic effectivity was noticed for H2 manufacturing for all samples. The faradaic effectivity values for Cl2 manufacturing for 5 completely different BiVO4/WO3 samples are offered in Supplementary Desk 1. For the most effective performing BiVO4/WO3 electrode, a photocurrent-to-Cl2 faradaic effectivity of 85% was noticed, with a mean faradaic effectivity of 74%, the best reported up to now for a secure low-cost system using earth ample supplies (Supplementary Desk 2). The absence of measurable O2 within the anode compartment signifies that the sub-100% (74% averaged over 5 BiVO4/WO3 electrodes) faradaic effectivity obtained for Cl2 manufacturing is probably going as a result of guide sampling methodology. This was additional corroborated by measuring faradaic effectivity of the method in darkish utilizing Pt because the working electrode. Beneath related working situations (i.e. at pH 1 NaCl at 2 mAcm−2), the Pt electrodes yielded a mean faradaic effectivity of 76% for chlorine manufacturing practically equivalent to that of the BiVO4/WO3 photoanodes (Supplementary Desk 1).

Fig. fourFig. 4

Product Quantification. Photogenerated Cl2 and H2 measured over the course of two h beneath 1 solar illumination. Inset exhibits faradaic effectivity for H2 and Cl2 manufacturing. Error bars signify the usual deviation for 5 completely different samples


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