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. 2021 Jan 9;24(2):102056. doi: 10.1016/j.isci.2021.102056

Ambient sunlight-driven photothermal methanol dehydrogenation for syngas production with 32.9 % solar-to-hydrogen conversion efficiency

Xianhua Bai 1,7, Dachao Yuan 4,7, Yaguang Li 1,∗, Hui Song 2,∗∗, Yangfan Lu 5, Xingyuan San 1, Jianmin Lu 6, Guangsheng Fu 1, Shufang Wang 1, Jinhua Ye 2,3,8,∗∗∗
PMCID: PMC7841357  PMID: 33537660

Summary

Methanol dehydrogenation is an efficient way to produce syngas with high quality. The current efficiency of sunlight-driven methanol dehydrogenation is poor, which is limited by the lack of excellent catalysts and effective methods to convert sunlight into chemicals. Here, we show that atomically substitutional Pt-doped in CeO2 nanosheets (Pts-CeO2) exhibit excellent methanol dehydrogenation activity with 500-hr level catalytic stability, 11 times higher than that of Pt nanoparticles/CeO2. Further, we introduce a photothermal conversion device to heat Pts-CeO2 up to 299°C under 1 sun irradiation owning to efficient full sunlight absorption and low heat dissipation, thus achieving an extraordinarily high methanol dehydrogenation performance with a 481.1 mmol g−1 h−1 of H2 production rate and a high solar-to-hydrogen (STH) efficiency of 32.9%. Our method represents another progress for ambient sunlight-driven stable and active methanol dehydrogenation technology.

Subject areas: Catalysis, Chemical Reaction Engineering, Chemistry

Graphical abstract

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Highlights

  • •

    Atomically substitutional Pt-doped CeO2 is active and robust for CH3OH dehydrogenation

  • •

    The photothermal conversion device can heat Pts-CeO2 to 299°C under 1 sun irradiation

  • •

    The joint system achieves a one sun irradiated H2 production rate of 481.1 mmol g−1 h−1

  • •

    This system delivers a high solar-to-H2 efficiency of 32.9% under one sun irradiation

Catalysis; Chemical Reaction Engineering; Chemistry

Introduction

Owing to the intermittent nature of energy production by renewable sources such as wind and solar energy, the new method to store and transport energy is significant for sustainable industrial implementation of renewable energy technologies. Reversible energy storage in the form of stable and transportable chemicals like methanol can address these challenges (Govindarajan et al., 2020). Methanol dehydrogenation can produce syngas (a mixture of H2 and CO) that has diverse applications (Dry, 2002; Khodakov et al., 2007). Syngas can not only contribute to electricity generation, transportation fuel production, and replacement for gasoline (Asthana et al., 2017; Paulino et al., 2020; Wang et al., 2020) but also serve as a vital chemical intermediate resource for the production of hydrogen via water-gas shift reaction, hydrocarbons via Fischer-Tropsch synthesis, ammonia via Haber-Bosch process, and higher chain alcohols/aldehydes via oxo-process (Huber et al., 2006). On the other hand, methanol dehydrogenation requires high operating temperatures due to the endothermic reaction nature, consuming a lot of energy restricting its application (Palo et al., 2007; Sordakis et al., 2018). As the most green and sustainable energy, solar-driven hydrogen generation from methanol is an attractive strategy to save the nonrenewable energy while storing solar energy (Huang et al., 2019; Liu et al., 2016, 2018; Wang et al., 2018b). So far, the efficiency of sunlight-driven methanol dehydrogenation via photocatalytic and photothermal synergistic strategies is difficultly improved due to the limitations in photogenerated carriers' transfer (Liu et al., 2016), sunlight absorption, and reactivity (Chen et al., 2010; Kudo and Miseki, 2009; Xiao and Jiang, 2019). As far as we known, the state of the art of sunlight-driven hydrogen production rate from methanol dehydrogenation is ∼0.2 mmol g−1 h−1 (Pang et al., 2019), far behind the demands of industrialization. Therefore, it is a great challenge to develop an innovative and sustainable solar-driven system that is highly efficient, stable, and low-cost to generate H2 and CO from methanol without additional energy input.

Except photocatalytic and photothermal synergistic strategies (Chai et al., 2016; Wang et al., 2018c), directly converting sunlight into thermal energy to drive catalytic reactions, namely sunlight-driven thermal catalysis, is another promising route to efficiently store solar energy into chemicals (Li et al., 2019; O'Brien et al., 2018), as black materials can absorb almost all the sunlight, from UV to infrared (IR) light, and convert it to thermal energy (Bae et al., 2015; Oara Neumann et al., 2013). However, the temperatures of black materials under natural sunlight irradiation are usually lower than 100°C due to the serious dissipation of thermal energy (Xu et al., 2017; Zeng et al., 2014), making it difficult to initiate methanol dehydrogenation (requiring 200°C to drive this reaction) (Brown and Gulari, 2004; Marbán et al., 2010; Mostafa et al., 2009). Our recent work of using selective light absorber to construct a photothermal conversion system is able to convert dispersed solar energy to high temperature (∼288°C), which provides the potential of realizing natural sunlight-driven methanol dehydrogenation reaction (Li et al., 2019). Additionally, exploring efficient and stable catalysts to produce hydrogen from methanol dehydrogenation at mild operating temperatures is also crucial. Recently, single-atom catalysts have shown extraordinary activities in various reactions, e.g., CO2 reduction (Yang et al., 2018; Zhao et al., 2017), oxygen reduction reaction (Chen et al., 2017), ethanol oxidation (Wang et al., 2017), owing to the maximum atom-utilization efficiency and unique electronic features. In order to make single-atom catalysts practical, the preparation of single atoms with high loading amounts is a basic factor. However, the dense single atoms in thermal catalysis are generally not stable under realistic reaction conditions due to their active nature (Qiao et al., 2011; Wei et al., 2014). Exploring highly stable and active dense single atom catalysts are thus the key to achieve practical solar-driven hydrogen generation from methanol.

In this work, in order to achieve efficient methanol dehydrogenation with high STH conversion efficiency under only one sun irradiation, we first developed a bimetal metal ions adsorption strategy to synthesize Pt single atoms on CeO2 nanosheets (Pts-CeO2) with a high Pt content (7.4 at%) and a lattice substituted single atom structure. The experimental and theoretical results evidently showed that lattice confinement strategy leads to both high activity and robust structure stability for methanol dehydrogenation during long-term operation. Then an improved photothermal conversion device was constructed, which could heat Pts-CeO2 to 299°C under one sun irradiation. As a result, the joint system gives rise to an unprecedented ambient sunlight-driven methanol dehydrogenation performance in terms of hydrogen production rate (481.1 mmol g−1 h−1), solar-to-H2 (STH) efficiency (32.9%), and stability (700 hr).

Results and discussion

Synthesis of substitutional Pt single atoms in CeO2 nanosheets

Pt single atoms have been demonstrated to be efficient for methanol dehydrogenation (Wang et al., 2018a). However, oxide-supported Pt single atoms synthesized by the impregnation method generally show the aggregation of Pt species to form Pt nanoparticles when annealing at high temperatures with high loading amounts. Figure S1A shows the atomic-scale scanning transmission electron microscope (STEM) images of 7.1 at% Pt-loaded on CeO2 nanosheets prepared by impregnation method and annealed at 450°C. It is clear that the Pt species were aggregated as nanoparticles (5 nm, denoted as Pt/CeO2 450) rather than Pt single atoms. To overcome this problem, we developed a bimetal deposition method with graphene oxides as the template to synthesize substitutional Pt-doped CeO2 nanosheets in single atomic form (Pts-CeO2) (Gao et al., 2017). As shown in Figure 1A, graphene oxides nanosheets were first dispersed into the aqueous solution containing soluble Pt, Ce precursors. Then, the mixture was freeze-dried to deposit the Pt and Ce metal ions on the surface of graphene oxides (Figure 1A). As Pt and Ce precursors were uniformly deposited on graphene oxides, the sample was annealed at 450°C to remove the graphene oxides and form the Pt-doped CeO2 nanosheets (denoted as Pts-CeO2) (see Figure S2). X-ray diffraction patterns show only diffraction peaks of CeO2, and no peak assigned to metallic Pt on Pts-CeO2 (see Figure S3A) (Kong et al., 2020). Energy-dispersive X-ray spectroscope (EDS) shows that the molar content of Pt was 7.4 at% (see Figure S3B). Transmission electron microscope (TEM) images reveal that Pts-CeO2 had nanosheet morphology with a mesoporous structure (Figures 1B and 1C). Figure S4 illustrates 3.1-nm thickness of the nanosheet. STEM-EDS shows that Pt and Ce elements were uniformly distributed over nanosheets (Figure 1D). The atomic-scale STEM image in Figure 1E demonstrates that bright dots were distributed in CeO2. This suggests that the 7.4 at% of Pt maintained the single atomic form in Pts-CeO2, revealing the capacity of this method for preparing dense Pt single atoms (Figure 1E).

Figure 1.

Figure 1

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Schematic illustration of synthesis and structure characterization of Pts-CeO2

(A) Schematic illustration of the synthesis of Pts-CeO2.

(B–D) (B and C) TEM images and (D) EDS mappings of Pt (yellow), Ce (cyan), and O (red) of Pts-CeO2.

(E) Atomic scale STEM image of Pts-CeO2. The inset image in Figure 1E is the SAED pattern.

(F) FT-EXAFS spectra of Pt L3-edge from Pts-CeO2, Pta-CeO2, Pt/CeO2 450, and Ce K-edge from Pts-CeO2.

(G) The FT-EXAFS curves of the proposed Pts-CeO2 structure (blue line) and the measured Pts-CeO2 (red line). Inset is the proposed model of Pts-CeO2 architecture.

We further characterized the structure difference between Pts-CeO2 and Pt single atoms synthesized by surface impregnation method (Pta-CeO2). Different from the random dispersion of Pt single atoms in Pta-CeO2 (see Figure S1B), the STEM image in Figure 1E clearly shows that Pt atom was located in the lattice position of Ce atom, indicating a substitutional doping mode of Pt in Pts-CeO2. To confirm the coordination structure of Pt in Pts-CeO2, the extended X-ray absorption fine structure (EXAFS) of Pt in Pts-CeO2 was investigated, in comparison with Pta-CeO2 and Pt/CeO2 450. Fourier transformed EXAFS (FT-EXAFS) of the Pt L3-edge shows that the peak of Pt in Pts-CeO2 was different from the curve of Pta-CeO2 (Figure 1F and Table S1) and Pt/CeO2 450, and was similar to the curve of Ce in Pts-CeO2, suggesting the existence of Pt-O and Pt-Ce coordination in Pts-CeO2. The EXAFS simulation (Table S1) shows that the coordination number of Pt-O in Pts-CeO2 was 7.3, larger than that of Pt in Pta-CeO2 (4.9). Further, Figure 1G shows that the simulated FT-EXAFS curve of proposed Pt-doped CeO2 model was also well fitted to the curve of Pts-CeO2. These results confirm that Pt was indeed substitutionally doped in CeO2 nanosheets in single atom form, agreeing well with the STEM result. Therefore, the lattice substitution structure was able to allow the high density of Pt single atoms in Pts-CeO2 to maintain good thermal stability. The Brunauer-Emmett-Teller specific area of Pts-CeO2 was 278.5 m2 g−1 (see Figure S5), ensuring numerous active sites for methanol dehydrogenation. X-ray photoelectron spectroscope (XPS) analysis shows that the Pt 4f7/2 peak of Pts-CeO2 was at 72.3 eV (see Figure S6), higher than that of the normal metallic Pt0 4f7/2 state (70.9 eV) (Qiao et al., 2011), indicative of the oxidation state of Pt single atoms in Pts-CeO2, which might be originated from the substitutional doped structure of single atoms.

Hydrogen production performance from methanol dehydrogenation over Pts-CeO2

As the catalytic activity of CeO2 nanosheets can be neglected (see Figure S7), we tested the thermocatalytic methanol dehydrogenation (CH3OH → 2H2 + CO) performance of Pt species in Pts-CeO2 and Pt/CeO2 450. Compared with Pt/CeO2 450, Pts-CeO2 displayed considerably high catalytic performances (Figure 2A). At the temperature of 150°C, the signals of carbon monoxide and hydrogen were detected over Pts-CeO2 but not over Pt/CeO2 450. As temperature was increased to 300°C, the hydrogen generation rate was increased to 111.02 mol g−1Pt h−1 over Pts-CeO2, equaling to H2 turnover frequency (TOF) of 21,658 hr−1, which was approximately 11 times that of Pt/CeO2 450 (10.19 mol g−1Pt h−1, 1988 h−1 of TOF, see Figures 2A and S8). The generation rate of CO was 0.5 times of H2 at different temperature over Pts-CeO2 and methanol conversion reached ∼6.0% at 300°C (see Figure S9). The methanol dehydrogenation activity of dense Pt single atoms anchored on CeO2 nanosheets (Pta-CeO2) are reduced sharply at operating temperature of 300°C (see Figure S10A) and the Pt single atoms will be aggregated as Pt nanoparticles after long-term operation (see Figure S10B). Methanol dehydrogenation stability of Pts-CeO2 was evaluated at 300°C for up to 504 hr. As shown in Figure 2B, the hydrogen generation rate of Pts-CeO2 was sloshed from 106.58 to 126.74 mol g−1Pt h−1, with no obvious decay trend (Figure 2B). The atom scale STEM (inset image in Figure 2B) and XPS spectrum (see Figure S11) of Pts-CeO2 after 504 hr reaction showed that the Pt single atoms were not precipitated and the chemical state of Pt remained stable. In addition, TEM image (see Figure S12) shows that Pts-CeO2 maintained the nanosheet structure after reaction. These results reveal the robust durability and stability of Pts-CeO2 in methanol dehydrogenation.

Figure 2.

Figure 2

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Thermal catalytic activities of Pts-CeO2 and reaction routes

(A) Hydrogen production rate from methanol in terms of Pt from Pts-CeO2 and Pt/CeO2 450 at different temperature.

(B) Methanol dehydrogenation stability of Pts-CeO2 at 300°C. The inset image in Figure 2B is the atomic scale STEM of Pts-CeO2 after methanol dehydrogenation.

(C) Structural evolution of Pt and CeO2 in Pta-CeO2 and Pts-CeO2 forms.

(D) Energy profiles for CH3OH decomposed as H atoms and CO on Pts-CeO2 (100) and Pt (111) surfaces. X axis illustrates the intermediates and reaction transition states (TSs); the Y axis illustrates the energy values of each state. The scale bar in (B) is 5 nm.

The thermal stability and methanol dehydrogenation mechanism of Pts-CeO2 was examined by density functional theory (DFT) theoretical simulations. The DFT results show that the formation energy of Pt single atoms anchored on CeO2 (Pta-CeO2 mode) and doped in CeO2 lattice (Pts-CeO2 mode) is −4.53 and −6.08 eV per Pt atom, respectively (see Figures 2C and S13). This confirms that the Pts-CeO2 is a more thermodynamically stable structure, which is the reason for robust of Pts-CeO2 in methanol dehydrogenation. We also calculated the methanol dehydrogenation pathways of Pts-CeO2 in comparison with metallic Pt nanoparticles (see Figures S14 and S15). As the Pt atoms in Pts-CeO2 are coordinated to lattice oxygens, the electrons are accumulated to lattice oxygens, which results in the positive theoretical oxidation state (+2.7) of Pt, much higher than that of metallic Pt (+0.42). As shown in Figure 2D, the ability of Pt sites in Pts-CeO2 for adsorbing methanol (−1.27 eV) is higher than that in Pt nanoparticles (−0.71 eV), revealing the strong methanol adsorption ability of high valence Pt. Detailed decomposition-pathway calculations (Figure 2D) show that the energy barrier for complete CH3OH dissociation to CO∗+4H∗ over Pts-CeO2 and Pt surface is 0.65 and 0.82 eV, respectively, and the rate-determining step is the decomposition of CH3OH∗ to CH3O∗+H∗. This result indicates that the CH3OH decomposition is kinetically more favorable on Pts-CeO2. The high adsorption ability and low energy barrier lead to the high activity of Pts-CeO2 for methanol dehydrogenation (Lin et al., 2017; Wang et al., 2019).

Configuration of photothermal conversion device

Ambient sunlight-driven methanol dehydrogenation without additional heat energy input is a sustainable way to produce hydrogen and simultaneously solar energy into chemicals. However, the temperatures of catalysts were generally below 100°C under one sun irradiation (1 kW·m−2); such low temperatures were unable to drive catalytic methanol dehydrogenation. We have recently shown that the temperature of catalysts could amount to ∼288°C under one sun irradiation with the assistance of a photothermal conversion device (Li et al., 2019). To obtain a high temperature under one sun irradiation, we further improved the photothermal conversion device. As shown in Figure 3A, the spectrally selective coating (TiONx) was coated on a quartz reaction tube (inner diameter: 7 mm, length: 500 mm) to construct a photothermal conversion device for the purpose of creating high temperature (see Figures S16–S18). Compared with the typical photothermal material graphene foam (see Figure S19) that absorb not only full spectrum of sunlight but also deep (IR) light ranging from 3 to 20 μm (Figure 3B) (Ren et al., 2017; Zhang et al., 2017), spectrally selective coating could strongly absorb sunlight but few IR light (Figure 3B), indicating that it is able to fully absorb sunlight with little IR radiation (Li et al., 2019). Kirchhoff's law illustrates that the IR absorptivity corresponds to the IR radiation capacity of materials (Dao et al., 2015). Therefore, most of heat energy originated from light is dissipated by IR radiation from graphene foam but not from spectrally selective coating (Ghasemi and Ranjbar, 2017). Moreover, a polished Cu film (see Figure S16) was also coated on the tube as shown in Figure 3A, aiming to reflect the IR radiation from the tube and catalysts to block thermal radiation output as shown in Figure 3C (Crawford and Treloar, 2004). In addition to inhibit IR radiation, a vacuum layer (1.7 × 10−3 Pa) was introduced to cover the whole reaction tube to eliminate the heat loss by conduction (Figure 3A). As a result, the inner temperatures of this device (Figure 3D) were consistently much higher than graphene foam under irradiation of sunlight with different intensities (the ambient temperature was 30°C, unless otherwise stated). The maximum inner temperature of this device reached 305°C under 1 sun irradiation (Figure 3E), while only 86°C was obtained from graphene foam by same light irradiation (Figure 3D). In addition, the maximum temperature of this device is around 180°C under 1 sun irradiation without coating Cu film.

Figure 3.

Figure 3

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Photothermal system

(A) Schematic of the new photothermal conversion device used for sunlight-driven hydrogen generation form methanol.

(B) Normalized light absorption spectra of the spectrally selective coating and graphene foam ranging from 0.4 to 20 μm.

(C) Sunlight absorption and IR radiation diagram of the new photothermal conversion device shown in Figure 3A.

(D) The temperature of new photothermal conversion device and graphene foam under different sunlight irradiation.

(E) The cross-sectional IR mapping of new photothermal conversion device under one sun irradiation obtained by an IR camera.

Ambient sunlight-driven hydrogen production from methanol

We loaded Pts-CeO2 in the photothermal conversion device and tested the sunlight-driven methanol dehydrogenation performance. As shown in Figure 4A, the new photothermal conversion device can heat Pts-CeO2 to 299°C under one sun irradiation (1.0 kW·m−2) (see Figures S20 and S21), while the temperature of Pts-CeO2 was only 78°C when it was directly irradiated by the same light intensity. The high temperature ensures the operation of methanol dehydrogenation. Hydrogen was even detected under only 0.2 kW·m−2 of sunlight irradiation and hydrogen production rate reached 481.1 mmol g−1 h−1 under 1.0 kW·m−2 of sunlight irradiation with methanol conversion (see Figure S22), corresponding to 1964.6 L m−2 h−1 hydrogen output (Figure 4B), whereas the Pts-CeO2 cannot decompose the methanol directly irradiated by one sun (see Figure S23). The STH conversion efficiency gradually increased with the intensity of sunlight irradiation and amounted to 32.9% under one sun irradiation (see Figures 4C, S24, and S25). The high STH conversion efficiency obtained at 30°C under 1 sun irradiation is higher than that of other photothermal catalytic systems and was even higher than the value of photo-electric energy conversion efficiency of benchmark Si solar cell (∼26%) (Bi et al., 2016). The durability of this photothermal conversion device-supported Pts-CeO2 system was tested under one solar irradiation. Figure 4D shows that the hydrogen production rate fluctuated between 1736 L m−2 h−1 and 2186 L m−2 h−1 without downward trend for as long as 744 hr, demonstrating excellent long-term stability. The morphology of Pts-CeO2 nanosheets also remained stable after reaction (see Figure S26).

Figure 4.

Figure 4

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Photothermal catalytic activity of Pts-CeO2

(A) The temperature of Pts-CeO2 loaded in the new photothermal conversion device (Pts-CeO2 + device, red) and in the normal quartz tube (Pts-CeO2, light blue), respectively, under different sunlight irradiations.

(B and C) Hydrogen generation rate and STH efficiency of Pts-CeO2 + device under different sunlight irradiations.

(D) Continuous one sun-driven methanol dehydrogenation performance for 744 hr.

Conclusion

In this work, we developed a bimetal deposition method with graphene oxides as the template to synthesize 7.4 at% of Pt single atoms substitutional doped CeO2 nanosheets (Pts-CeO2). Pts-CeO2 showed a high hydrogen generation rate of 111.02 mol g−1Pt h−1 from methanol dehydrogenation at 300°C, excellent thermal stability and 500 hr level catalytic stability due to the lattice substitution structure of Pt single atoms. Further, a novel photothermal conversion device constructed by Cu film to block IR radiation output, spectrally selective coating to absorb sunlight with little IR radiation and vacuum layer to minimum heat conduction loss, were used to heat Pts-CeO2 to 299°C under one standard solar irradiation at 30°C of ambient temperature. Under 1 sun irradiation, the new photothermal conversion device supported Pt-CeO2 showed a hydrogen production rate of 476.6 mmol g−1 h−1 or 1946 L m−2 h−1 from methanol with a month level stability, corresponding to STH efficiency of 32.9%. Our strategy of combining efficient single atom catalysts and photothermal conversion device demonstrates a potential efficient ambient sunlight-driven hydrogen generation strategy from methanol without additional energy input and may be applicable to other catalytic reactions to realize efficient solar to chemical energy conversion.

Limitations of the study

Here, we carried out experiments of sunlight-driven photothermal methanol dehydrogenation for syngas production with 32.9% STH conversion efficiency in our laboratory, where the produced toxic CO can be well handled. Due to the concerns about producing large amounts of toxic CO, it is unfeasible for us to perform the outdoor experiments using the current photothermal device. However, considering that the production of syngas is already very mature in industry, we believe that the outdoor experiments could be viable by improving the experimental equipment.

Resource availability

Lead contact

Further information and requests for resources and materials should be directed to and will be fulfilled by the lead contact, Jinhua Ye (Jinhua.YE@nims.go.jp).

Materials availability

All chemicals were obtained from commercial resources and used as received.

Data and code availability

There is no data set or code associated with this work.

Methods

All methods can be found in the accompanying Transparent methods supplemental file.

Acknowledgments

This work is supported by the National Natural Science Foundation of China (Grant Nos. 51702078 and 21633004), Hebei Provincial Department of Education Foundation (Grant No. BJ2019016), Outstanding Doctoral Cultivation Project of Hebei University (YB201502), JSPS KAKENHI (No. JP18H02065), the Photo-excitonix Project at Hokkaido University, the World Premier International Research Center Initiative (WPI Initiative) on Materials Nanoarchitectonics (MANA), MEXT (Japan). Thanks for the TEM technical supports provided by the Microanalysis Center, College of Physics Science and Technology, Hebei University. We acknowledge the Shanghai Synchrotron Radiation Facility for conducting the EXAFS experiment (BL14W1).

Author contributions

Conceptualization, Y. G. Li, H. Song and J. H. Ye.; Resources, Y. G. Li, X. H. Bai and D. C. Yuan Investigation, X. H. Bai; Formal Analysis, J. M. Lu., Y. F. Lu and X. Y. San; Writing – Original Draft Y. G. Li and H.S.; Writing – Review & Editing Y. G. Li, H. S., F. Wang and G. S. Fu. Supervision, J. H. Ye.

Declaration of interests

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Published: February 19, 2021

Footnotes

Supplemental information can be found online at https://doi.org/10.1016/j.isci.2021.102056.

Contributor Information

Yaguang Li, Email: liyaguang@hbu.edu.cn.

Hui Song, Email: song.hui@nims.jo.jp.

Jinhua Ye, Email: jinhua.ye@nims.go.jp.

Supplemental information

Document S1. Transparent methods, Figures S1–S26, and Tables S1–S3
mmc1.pdf (1.9MB, pdf)

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Associated Data

This section collects any data citations, data availability statements, or supplementary materials included in this article.

Supplementary Materials

Document S1. Transparent methods, Figures S1–S26, and Tables S1–S3
mmc1.pdf (1.9MB, pdf)

Data Availability Statement

There is no data set or code associated with this work.

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