Chemistry

Enhanced photocatalytic efficiency of a Ti-based metal-organic framework for hydrogen manufacturing: Hybridization with ZnCr-LDH nanosheets

Over the previous many years, the speedy depletion of fossil fuels and the incidence of environmental air pollution have raised consciousness to the largest disaster that people have ever confronted. To beat it, many efforts have been steadily made within the technological improvement of other clear power and environmental remediation utilizing sustainable power sources, reminiscent of solar, wind, geothermal energy, etc1. Amongst them, visible-light photocatalytic know-how utilizing photo voltaic power could be very promising for power and environmental points resulting from its abundance, ease of use, and eco-friendliness1,2,Three.

Metallic-organic frameworks (MOFs), comprised of steel ions and natural ligands, have obtained vital consideration due to their distinctive structural traits together with extremely ordered and nanoporous networks4. Thus, MOFs have quite a few potential purposes in fuel storage, fuel separation, sensing, and catalysis5,6,7,eight. Furthermore, in recent times, MOFs as photocatalysts for hydrogen (H2) manufacturing primarily based on water photolysis have obtained appreciable attention9,10,11,12,13,14. Among the many numerous MOF-based photocatalysts, NH2-MIL-125(Ti) (Supplementary Data, Fig. S1), which consists of cyclic Ti8O8(OH)four octamers and 2-aminoterephthalic acid, possesses a slim band hole of two.5 eV and has been reported as a possible photocatalyst that is ready to produce hydrogen beneath visible-light irradiation15,16,17,18,19. Nonetheless, as a result of inefficient cost switch, gentle absorption, and photo-chemical stability, the photoactivity of NH2-MIL-125(Ti) in direction of hydrogen manufacturing from water just isn’t very efficient as compared with conventional semiconductor photocatalysts17,18,19,20. Due to this fact, it stays an essential problem to enhance the photocatalytic efficiency of NH2-MIL-125(Ti) photocatalysts. One of many viable methods to reinforce the photocatalytic exercise of NH2-MIL-125(Ti) is to hybridize it with different semiconducting photocatalysts; such a hybridization can facilitate electron switch between two elements, and thus, the photocatalytic exercise of the MOF could be enhanced21,22.

Herein, we report novel NH2-MIL-125(Ti)-based hybrid composites that present enhanced visible-light photocatalytic exercise in direction of hydrogen manufacturing primarily based on water photolysis. The hybrid composites are ready by the hybridization of NH2-MIL-125(Ti) and layered double hydroxides (LDHs) with a two-dimensional construction. In fact, totally different composites of MOF/0D-semiconductors and/or MOF/2D-graphene as photocatalysts for water remediation have been reported in latest research23,24. Nonetheless, a number of reviews on hydrogen manufacturing by way of water photolysis utilizing MOF-based hybrid composites have been reported17,18,19,20,22. Very just lately, hybrid composites of MOFs and LDHs have been examined as fuel and water adsorbents25,26. To the very best of our information, nonetheless, there was no report on enhancing photocatalytic hydrogen manufacturing by way of the hybridization of MOFs and LDHs.

On this work, ZnCr-LDH, which is comprised of Zn2+ and Cr3+ ions, was used. This materials has been reported as a really promising photocatalyst with a slim band hole of two.6 eV and the suitable valence band place to oxidize water27. At 420 nm, its quantum effectivity is above 60%, and the fabric reveals a wonderful photo-chemical stability27. Due to this fact, it was believed that the hybridization of NH2-MIL-125(Ti) with ZnCr-LDH would lead to a positively synergetic impact to enhance the photocatalytic effectivity beneath visible-light irradiation.

Hybrid composites of NH2-MIL-125(Ti) and ZnCr-LDH nanosheets (NSs) had been synthesized by rising NH2-MIL-125(Ti) within the presence of exfoliated ZnCr-LDH NSs, as illustrated in Scheme 1a. It has been reported that LDHs could be ready as a colloidal suspension of individually exfoliated NSs in a non-aqueous solvent (i.e., formamide)28,29,30. Sometimes, NH2-MIL-125(Ti) is synthesized in the same solvent reminiscent of dimethylformamide (DMF, Scheme 1b)17,31. With this understanding of the response medium, the nanosheet colloids had been first induced from bulk ZnCr-LDH in a blended non-polar resolution (DMF/MeOH, 50:50 wt%).

Pristine ZnCr-LDH in its nitrate kind was ready by the co-precipitation technique30. From powder X-ray diffraction (powder XRD), it was confirmed that the synthesized ZnCr-LDH reveals typical Bragg reflection patterns of the hexagonal part ions (Supplementary Data, Fig. S2a). Area-emission scanning electron microscopy (FE-SEM) photos reveal a plate-like morphology of submicron dimension for the pristine ZnCr-LDH, as proven in Fig. 1a. The colloidal suspension of exfoliated ZnCr-LDH NSs was obtained within the blended resolution of DMF/MeOH by alternatively performing ultrasonication and vigorous stirring. The resultant colloidal suspension has a bright-purple color, and clearly exhibits the Tyndall phenomenon by laser illumination (Supplementary Data, Fig. S3a). This result’s indicative of the presence of tiny particles within the solvent. The Zeta potential measurement of the exfoliated ZnCr-LDH NSs reveals a constructive worth of roughly 23 mV (Supplementary Data, Fig. S3b). This worth signifies that ZnCr-LDH NSs have a positively charged floor, which is in settlement with the beforehand reported consequence30. For the exfoliated ZnCr-LDH NSs, the transmission electron microscopy (TEM) photos present a plate-like morphology with a really skinny thickness (Figs 1a, and S4a). Not like that of the majority ZnCr-LDH, no powder XRD sample of the exfoliated ZnCr-LDH NSs is noticed, as they sometimes present an amorphous construction (Supplementary Data, Fig. S2b). This result’s as a result of lack of long-range stacking within the c-axis28,29,30. Nonetheless, the chosen space electron diffraction (SAED) picture clearly exhibits that the exfoliated ZnCr-LDH NSs current hexagonal spots (Supplementary Data, Fig. S4b). This sample clearly signifies that the crystal construction of ZnCr-LDH NSs stays undecomposed after the exfoliation response28,29,30. The hybrid composites of NH2-MIL-125(Ti) and ZnCr-LDH NSs had been synthesized by placing the precursors of NH2-MIL-125(Ti) into the colloidal suspension of ZnCr-LDH NSs and continuing with the solvothermal response. To seek out the optimum efficiency of photocatalytic hydrogen manufacturing, a collection of hybrid composites had been ready by controlling the burden of ZnCr-LDH powder (50, 100, 200, and 400 mg) used for the colloidal suspension of ZnCr-LDH NSs, and the obtained hybrid composite samples had been named as ML50, ML100, ML200, and ML400, respectively.

Determine 1Figure 1

Illustration of the syntheses of (a) hybrid composites of NH2-MIL-125(Ti) and ZnCr-LDH NSs and of (b) pristine NH2-MIL-125(Ti). FE-SEM photos corresponding to every determine are additionally proven.

The crystal constructions and part purities of the synthesized hybrid composites had been examined by powder XRD patterns. As plotted within the left panel of Fig. 2, the powder XRD sample of pristine NH2-MIL-125(Ti) ready with out ZnCr-LDH NSs matches properly with the simulated one, and impurity peaks, reminiscent of these of TiO2, usually are not noticed. After the hybridization with ZnCr-LDH NSs, the powder XRD profiles exhibit solely NH2-MIL-125(Ti) peaks, whatever the totally different quantities of ZnCr-LDH NSs apart from ML400. This means that ZnCr-LDH NSs are homogeneously distributed within the current composite supplies. Within the case of ML400, nonetheless, reflection peaks of ZnCr-LDH equivalent to the (003) and (006) planes had been noticed, as proven in the precise panel-top of Fig. 2. These impurities are attributed to the truth that a portion of the majority ZnCr-LDH content material used for the preparation of ML400 couldn’t be exfoliated beneath our synthesis circumstances. An in depth inspection of XRD profiles reveals that the primary peak depth roughly 6.74° turns into suppressed with will increase within the quantity of ZnCr-LDH, as seen in the precise panel-bottom of Fig. 2. This phenomenon could also be attributed to the restricted crystallization of NH2-MIL-125(Ti) by ZnCr-LDH NSs throughout the formation of NH2-MIL-125(Ti).

Determine 2Figure 2

(Left panel) energy XRD patterns of (a) simulated NH2-MIL-125(Ti), (b) pristine NH2-MIL-125(Ti), (c) ML50, (d) ML100, (e) ML200, and (f) ML400. (Proper panel-top) The enlarged areas of (e,f) within the vary between 9.1° and 20.Three°. (Proper panel-bottom) The enlarged space of the primary peaks within the vary between 6.Three° and seven.1°.

To elucidate the affect of ZnCr-LDH NSs on the microscopic construction of NH2-MIL-125(Ti) throughout its crystal development, we monitored the morphology of the hybrid composites with FE-SEM. In Fig. 3a,b, as talked about, pristine ZnCr-LDH reveals a plate-like morphology of submicron dimension, whereas the exfoliated ZnCr-LDH NSs obtained by precipitation utilizing a high-speed centrifuge current a randomly stacked construction consisting of sheets a number of hundred nanometres in dimension. Within the case of pristine NH2-MIL-125(Ti) ready within the absence of ZnCr-LDH NSs, the SEM picture signifies a really common decahedron morphology of submicron dimension, as proven in Fig. 3c. In distinction, the morphology of all of the hybrid composites encompass a spherical disk-type form, and such a disk-shape turns into extra irregular with rising quantities of ZnCr-LDH NSs (Fig. 3d–g). For nearer inspection, the enlarged picture of the ML200 pattern proven in Fig. 3h reveals that NH2-MIL-125(Ti) is enwrapped by ZnCr-LDH NSs as a core-shell construction. This formation is much like the earlier consequence referring to diminished graphene oxide/MIL-125(Ti) composites22. Evidently, as the quantity of ZnCr-LDH NSs will increase, the crystal dimension and the crystallinity of NH2-MIL-125(Ti) turns into considerably smaller and poorer, respectively. This consequence agrees with that offered by the powder XRD information.

Determine ThreeFigure 3

FE-SEM photos of (a) pristine ZnCr-LDH; (b) exfoliated ZnCr-LDH NSs obtained through the use of a high-speed centrifuge; (c) pristine NH2-MIL-125(Ti); and hybrid composites: (d) ML50, (e) ML100, (f) ML200, and (g) ML400; (h) An enlarged picture of the ML200 pattern.

Additional, to extra clearly determine the hybrid-structural formation of NH2-MIL-125(Ti) and ZnCr-LDH NSs, TEM photos had been taken earlier than and after the hybridization. Determine four exhibits TEM photos of the pristine NH2-MIL-125(Ti) and ML 200 samples. As with the SEM picture proven in Fig. 3c, the TEM picture of pristine NH2-MIL-125(Ti) reveals a really common decahedron morphology (Fig. 4a,b). After hybridization, nonetheless, photos of the hybrid composite present that NH2-MIL-125(Ti) is enwrapped by a considerable amount of ZnCr-LDH NSs of a number of hundred nanometres in dimension (Figs 4c,d and S4a). As well as, HRTEM was employed to attempt to observe the formation of the hybrid construction. Though the lattice fringes are clearly noticed (Supplementary Data, Fig. S5b), there’s a extreme structural distortion attributable to the electron beam. The lattice distance proven in inset of Fig. S5b is calculated as zero.192 nm, equivalent to the (zero12) airplane of ZnCr-LDH. The discovering signifies that the crystallinity of ZnCr-LDH NSs stays unchanged after hybridization. Moreover, the SAED sample additionally presents extreme distortion, however the existence of a combination of spots and ring patterns is confirmed (Supplementary info, inset of Fig. S5a). It’s obvious that NH2-MIL-125(Ti) and ZnCr-LDH NSs exist in ML200.

Determine fourFigure 4

TEM photos of (a,b) pristine NH2-MIL-125(Ti) and (c,d) the ML200 pattern. (e) Elementary maps and the EDX spectrum of the ML200 pattern.

In accordance with the outcomes of powder XRD, SEM, and TEM, the formation technique of the hybrid composite of NH2-MIL-125(Ti)/ZnCr-LDH NSs could be proposed in 4 phases, that’s, the anchoring of negatively charged ligands on the floor of ZnCr-LDH sheets, nucleation and development by way of the response between steel ions (Ti4+) and ligands, and crystallization beneath the current response circumstances. The driving pressure behind the formation of the hybrid composite is attributed to the sturdy electrostatic interactions. As talked about, ZnCr-LDH NSs have a positively charged floor (Supplementary Data, Fig. S3b), and based on the earlier literature32,33, the zeta potential of NH2-MIL-125(Ti) represents a adverse cost (−20 to −30 mV). Certainly, when the ligand precursor is transferred into the colloidal suspension of the exfoliated ZnCr-LDH NSs, a flocculation phenomenon happens. This means the ionic mixture of a carboxylic group of the ligands and ZnCr-LDH NSs. Then, the steel ions (Ti4+) react with the opposite carboxylic group of the ligands. The hydrothermal response circumstances result in the nucleation and crystal development. Lastly, ZnCr-LDH NSs-enwrapped MOFs are generated, as illustrated in Fig. 1a. The alternative fees of those two supplies consequence within the sturdy coupling by electrostatic forces. Consequently, it’s sure that the ZnCr-LDH NSs act because the substrate for the crystal development of NH2-MIL-125(Ti) and have an effect on the crystal dimension and crystallization of NH2-MIL-125(Ti). Related phenomena have additionally been reported for 2D material-based composites34.

The floor space and porosity of the hybrid composites had been investigated with nitrogen adsorption-desorption isotherm evaluation (Supplementary Data, Fig. S6). The entire hybrid supplies exhibit a steep N2 adsorption within the low-pressure area of pp0−1 < 0.1, showing typical type I characteristics for a micropore structure35. Additionally, the plots present a distinct hysteresis at pp0−1 > zero.5, indicating the presence of mesopores35. The calculated particular floor space, whole pore quantity, micropore quantity, and mesopore quantity are summarized in Desk 1. Pristine NH2-MIL-125(Ti) exhibits a really giant floor space of 1550 m2g−1 with a excessive pore quantity of zero.636 cm2g−1, whereas ZnCr-LDH exhibits a considerably smaller floor space of 13 m2g−1. For the hybrid composites, all samples possess a bigger floor space than that of ZnCr-LDH, whereas the worth is markedly diminished as the quantity of ZnCr-LDH NSs will increase. It is very important notice that the lower in floor space has a adverse impact on the effectivity of catalytic reactions. As is understood for catalytic reactions, the floor space is a crucial issue that may enhance the catalytic effectivity as a result of a bigger floor space can present extra surface-active websites. With this in thoughts, we first carried out the examine on the photocatalytic hydrogen manufacturing of the current hybrid composites beneath visible-light irradiation.

Desk 1 Parameters taken from the nitrogen adsorption-desorption measurements.

Determine 5 exhibits the common outcomes of the three repeating photocatalytic assessments. To our shock, all of the hybrid supplies present a considerably enhanced photocatalytic efficiency for hydrogen manufacturing beneath visible-light irradiation, in comparison with that of pristine NH2-MIL-125(Ti) and ZnCr-LDH. Among the many hybrid composites, specifically, the ML200 pattern exhibits the very best catalytic efficiency for hydrogen manufacturing. From the outcomes of the hydrogen manufacturing take a look at, it is very important point out that hybridization with ZnCr-LDH NSs has the wonderful impact of compensating for the disadvantages, regardless of the floor areas of the hybrid composites being decrease than that of pristine NH2-MIL-125(Ti). However, the photocatalytic efficiency of ML400, with a big quantity ZnCr-LDH NSs, remarkably decreased. Such a deterioration in photocatalytic efficiency is attributable to the next information: to utterly exfoliate an extra of ZnCr-LDH to nanosheets is troublesome beneath the current circumstances. As seen from the outcomes of powder XRD (Fig. 2) and SEM (Fig. Three), an extreme quantity of ZnCr-LDH considerably reduces the crystallinity of NH2-MIL-125(Ti). Moreover, unexfoliated particles make the hybridization between the 2 elements inhomogeneous. For these causes, the BET floor space and whole pore quantity of ML400 are markedly decrease, as listed in Desk 1. As well as, a dense packing of extreme ZnCr-LDH on the floor of NH2-MIL-125(Ti) can cut back the lively websites of the NH2-MIL-125(Ti) photocatalyst. Consequently, the diminished photocatalytic efficiency of ML400 is the results of an ineffective hybridization of the 2 elements.

Determine 5Figure 5

Photocatalytic hydrogen evolution over the hybrid composites ML50 (), ML100 (Δ), ML200 (□), and ML400 (); pristine NH2-MIL-125(Ti) () and ZnCr-LDH (▲); and a bodily blended pattern of NH2-MIL-125(Ti) and ZnCr-LDH NSs (■) in aqueous options containing zero.01 M triethanolamine (TEOA), as a gap scavenger, and beneath visible-light irradiation. Experimental circumstances; photocatalyst: 30 mg, gentle supply: 300 W Xe lamp with a cut-off filter (λ > 420 nm). The error bars had been obtained by three measurements.

Extra importantly, on this take a look at, the current hybrid composites present excessive photocatalytic actions within the absence of noble metals, reminiscent of Pt, as a co-catalyst. In accordance with the literature, the photocatalytic exercise of NH2-MIL-125(Ti) for hydrogen manufacturing could be improved by roughly two occasions when Pt is used as a co-catalyst17. Within the current work, the common hydrogen manufacturing price of the ML200 hybrid composite is 127.6 mmol h−1 g−1 beneath visible-light irradiation, which is roughly Three-times greater than that of pristine NH2-MIL-125(Ti) (40.eight mmol h−1 g−1) and roughly 250-times greater than that of pristine ZnCr-LDH (zero.5 mmol h−1 g−1). The current values are roughly 1.5–2-times decrease than the outcomes reported for the Pt co-catalyst/NH2-MIL-125(Ti) system, however it’s noteworthy that the photocatalytic actions of the hybrid composites are achieved with out utilizing a treasured co-catalyst, reminiscent of Pt17. The current outcomes are believed to learn from the synergy of the sturdy coupling between NH2-MIL-125(Ti) and ZnCr-LDH NSs. Moreover, to substantiate this notion, a bodily blended pattern of NH2-MIL-125(Ti) and ZnCr-LDH NSs was ready by including NH2-MIL-125(Ti) powder to the colloidal suspension of ZnCr-LDH NSs, and the photocatalytic exercise was examined. As proven in Fig. 5, this pattern reveals a photocatalytic exercise (16.1 mmol h−1 g−1) even decrease than that of pristine NH2-MIL-125(Ti). This discovering verifies that there exists a robust chemical interplay between NH2-MIL-125(Ti) and ZnCr-LDH NSs within the hybrid composites. Based mostly on the photocatalytic performances, additional investigations had been carried out for the ML200 pattern.

To analyze the coexistence of NH2-MIL-125(Ti) and ZnCr-LDH NSs, elementary mapping and energy-dispersive X-ray spectroscopy (EDX) had been carried out (Fig. 4e). Elementary mapping photos and the EDX spectrum present that every transition steel factor of Zn, Cr, and Ti, along with N, exists and is distributed homogenously within the ML200 pattern. The molar ratio of Ti: Zn: Cr is 1: zero.75: zero.34, and subsequently, the molar ratio of /(Zn1−xCrx(OH)2) is set to be zero.17. As talked about beforehand, the existence of ZnCr-LDH NSs just isn’t verified by the powder XRD patterns. Due to this fact, to cross-confirm the HRTEM picture (Supplementary Data, Fig. S5b), Zn Okay- and Cr Okay-edge X-ray absorption near-edge spectroscopy (XANES) of the ML200 pattern was carried out (Supplementary Data, Fig. S7). The Zn Okay- and Cr Okay-edge XANES spectral shapes of the ML200 hybrid composite are fairly much like these of pristine ZnCr-LDH, indicating that the construction of ZnCr-LDH NSs stays intact after the hybridization. That is in good settlement with the consequence obtained from the HRTEM picture.

UV-vis diffuse reflectance spectra (DRS) had been obtained to characterize the band construction and optical properties of the ML200 hybrid composite as compared with these of every compound earlier than hybridization. As plotted in Fig. 6, pristine NH2-MIL-125 possesses one sturdy absorption peak at 2.76 eV equivalent to the ligand-to-metal-charge switch (LMCT) of the valence band (VB) composed of C 2p, N 2p, and O 2p orbitals → the conduction band (CB) composed of Ti 3d and O 2p orbitals18,36. Within the case of ZnCr-LDH, two sturdy absorption peaks at 1.71 eV for Cr 3dt2g → Cr Three deg (transition) and at 2.37 eV for the ligand-to-metal-charge switch (LMCT) of O 2p → Cr Three deg are noticed27,37. Upon the hybridization of the 2 supplies, the ML200 hybrid composite shows two absorption peaks at 1.54 nm and a pair of.69 eV within the seen area. The spectral distinction between earlier than and after the hybridization is attributed to the efficient digital coupling within the hybridization of the 2 supplies, that’s, an overlap happens between the d-d transition of chromium ions in ZnCr-LDH and that of titanium ions in NH2-MIL-125(Ti).

Determine 6Figure 6

UV-vis diffuse reflectance spectra of the ML200 hybrid composite (strong line) and unhybridized samples of NH2-MIL-125(Ti) (dashed line) and ZnCr-LDH (dotted line).

X-ray photoelectron spectroscopy (XPS) was carried out for the ML200 pattern. As proven in Fig. 7b, the Ti 2p binding power of the ML200 hybrid composite is shifted to the next binding power after the hybridization with ZnCr-LDH NSs. However, the binding energies of the Zn 2p and Cr 2p are negatively shifted, as proven in Fig. 7c,d. Additional, within the case of the XPS spectrum of the O 1 s, the general peak is barely shifted to the next binding power after hybridization (Fig. 7e). Such modifications within the binding energies are generated as a result of the electron density of NH2-MIL-125(Ti) decreases and that of ZnCr-LDH NSs will increase. These findings clearly point out that there exists an efficient digital coupling between the 2 elements due to the hybridization, resulting in not solely the harvest of extra incident photons to supply extra photo-generated electrons and holes but in addition the suppression of the recombination of photo-generated electron and gap pairs resulting from an efficient electron switch between NH2-MIL-125(Ti) and ZnCr-LDH NSs38,39.

Determine 7Figure 7

XPS spectra of (backside in a,b,e) pristine NH2-MIL-125(Ti), (backside in c,d) pristine ZnCr-LDH and (high in a–e) the ML200 hybrid composite: (a) the full-spectrum survey, (b) Ti 2p, (c) Zn 2p, (d) Cr 2p and (e) O 1 s.

As well as, FT-IR spectroscopy was carried out to show the hybridization of ZnCr-LDH NSs and NH2-MIL-125(Ti) (Supplementary Data, Fig. S8). Within the case of pristine ZnCr-LDH, sturdy and broad peaks centred at 3300–3600 cm−1 and 1635 cm−1 are noticed and are assigned because the O-H stretching vibration of the hydroxyl teams within the brucite layers and the H-O-H bending vibration of interlayer water molecules, respectively40. As well as, a attribute of ZnCr-LDH in its nitrate kind is exhibited as an absorption peak round 1340 cm−1 for the interlayer NO3− vibration band. The bands noticed beneath 700 cm−1 characterize Zn/Cr–OH and Zn–O–Cr stretching vibration modes40. Pristine NH2-MIL-125(Ti) and the ML200 hybrid composite exhibit related attribute bands: the carboxylic acid useful teams of NH2-MIL-125(Ti) within the area of 1380–1700 cm−1 and the vibrations of the O-Ti-O teams within the area of 400–800 cm−1 41. The ML200 hybrid composite exhibits all of the attribute peaks of ZnCr-LDH and NH2-MIL-125(Ti) round 3300–3600 cm−1, clearly confirming the presence of the 2 elements. Particularly, a robust band at 635 cm−1 equivalent to O-Ti-O is negatively shifted after the hybridization. This modification is as a result of lower within the electron density of NH2-MIL-125(Ti), which is in good settlement with XPS outcomes (Fig. 7). The current FTIR spectroscopy evaluation not solely strongly confirms the existence of the ZnCr-LDH and NH2-MIL-125(Ti) but in addition signifies that there’s an obvious digital interplay between the 2 supplies.

The efficient digital interplay between the 2 supplies was investigated by the photocurrent transient response measurement (Supplementary Data, Fig. S9). The photocurrent response beneath on-off gentle operation demonstrates that the photocurrent of the ML200 hybrid composite is significantly greater than that of pristine NH2-MIL-125(Ti) and ZnCr-LDH electrodes. This discovering is attributed to the efficient electron coupling led to by the hybridization of ZnCr-LDH and NH2-MIL-125(Ti). Consequently, the effectivity of the separation and switch of photogenerated electron–gap pairs is considerably improved.


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