paper9-si-acs-mater-lett-2024-ir-clusters-cu2o-n2-photofixation

SUPPORTING INFORMATION

Collaboration between Iridium Clusters and {111} Dominant Facet of Cu2O for Triggering Efficient N2

Photofixation

Wensheng Zhang[1] , Qingmei Tan[2] , Tianren Liu[2] , Zhishan Liang[1] , Youlin Huang[1] , Ying He[1] ,

Dongxue Han[1,2] *, Dongdong Qin[1] and Li Niu[1,3]

1School of Civil Engineering c/o Center for Advanced Analytical Science, School of Chemistry

and Chemical Engineering, Guangzhou University, Guangzhou 510006, P. R. China

2School of Chemistry and Chemical Engineering Guangzhou Key Laboratory of Sensing

Materials & Devices, Center for Advanced Analyti-cal Science, Guangzhou University,

Guangzhou 510006, P. R. China

3School of Chemical Engineering and Technology, Sun Yat-sen University, Zhuhai 519082, P.
R. China
*email: dxhan@gzhu.edu.cn

Supplementary Figures

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Figure S1 The NH4[+] detection via ion chromatography. a Ion chromatography data for different concentrations of NH4[+] . ( b, c ) standard curve.

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Figure S2 Screening of dominant of Cu2O. The photocatalytic N2 fixation performance of Cu2O100 and Cu2O-111 samples.

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Figure S3 The NH3 yield of over Cu2O-111-x% Ir catalysts under 2 h light radiation.

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Figure S4 Comparison of NH3 yield over various catalysts under 2 h illumination.

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Figure S5 XRD patterns of Cu2O-100 and Cu2O-111 samples.

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Figure S6 HRTEM images ( a, c ) and particle size distribution ( b, d ) of Cu2O-100 and Cu2O-111 samples.

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Figure S7 The TEM ( a ) and HAADF-STEM ( b, c ) images of Cu2O-100-Ir, and the corresponding STEM element mappings for Cu ( d ), O ( e ), and Ir ( f ).

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Figure S8 The TEM ( a ) and HAADF-STEM ( b, c ) images of Cu2O-111-Co, and the corresponding STEM element mappings for Cu ( d ), O ( e ), and Co ( f ).

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Figure S9 The TEM ( a ) and HAADF-STEM ( b, c ) images of Cu2O-111-Rh, and the corresponding STEM element mappings for Cu ( d ), O ( e ), and Rh ( f ).

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Figure S10 The fitting of FT-EXAFS spectra for Ir foil (a), IrO2 (b), and Cu2O-111-Ir (c) in R- space .

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Figure S11 The N2-TPD spectra of Cu2O-111, Cu2O-111-Co, Cu2O-111-Rh and Cu2O-111-Ir.

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Figure S12 The transient photocurrent response for the Cu2O-111-Ir sample under an Ar or N2 atmosphere.

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Figure S13 The EIS (a) and PL (b) spectra of different samples.

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Figure S14 UV-DRS and quantum efficiency of NH3 evolution by N2 photofixation for Cu2O111-Ir under monochromatic light of different wavelength.

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Figure S15 (a) UV-Vis absorption spectra of various N2H4 concentrations after incubated for 20 min at room temperature. (b) Calibration curve used for estimation of N2H4 concentration. The absorbance at 458 nm was measured by UV-vis spectrophotometer, and the fitting curve shows good linear relation of absorbance with N2H4 concentration ( y = 0.34713E-4 x + 0.01818, R[2] = 0.99975) of calibration curves. (c) UV-vis absorption spectra of reaction solution by different catalysts in the first 1 h. No N2H4 was detected at 458 nm.

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Figure S16 XRD (a), High-resolution Cu 2p (b), O 1s (c) and Ir 4f (d) spectra of Cu2O-111-Ir catalyst before and after photocatalytic N2 reduction reaction.

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Figure S17 TEM (a), HAADF-STEM (b) and STEM element mapping (c-f) images of the Cu2O-

111-Ir catalyst after cycling test.

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Figure S18 The specific designed reaction cell for in situ FT-IR experiments.

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Fig. S19 Mass spectral illustrations of the indophenol from diverse atmospheric conditions under 1 h illumination. (a) The mass spectral illustrations of the indophenol prepared from[14] N2 atmospheric conditions. (b) The mass spectra of the indophenol prepared from[15] N2 atmospheric conditions.

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Figure S20 DFT-established structures ( a, b ) and N2 adsorption configuration ( c, d ) of Cu2O-111Co and Cu2O-111-Rh (Color code: red, brick red, orange, cyan and blue green are Cu, O, Co, Rh, and N atoms, respectively).

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Figure S21 DFT calculations. a Adsorption energies of N2 over various catalysts. b N-N distance of free N2, *N-N on Cu2O-100-Ir, Cu2O-111-Ir, Cu2O-111-Co, and Cu2O-111-Rh samples.

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Figure S22 Work functions of Cu2O-100 ( a ), Cu2O-100-Ir ( b ), Cu2O-111 ( c ), Cu2O-111-Co ( d ), Cu2O-111-Rh ( e ) and Cu2O-111-Ir ( f ) samples, respectively.

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Figure S23 Gibbs free energy diagrams of N2 photofixation through different paths over Cu2O100-Ir (purple line represents the optimal NRR process, green line represents other possibilities of NRR paths); the insets are optimized atomic structure models of N2 adsorption and reduction on the Ir sites of Cu2O-100-Ir (Color code: red, brick red, grayish blue, blue and green are Cu, O, Ir, N, and H atoms, respectively; asterisk for activated site).

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Figure S24 The sealed photocatalytic N2-fixation reactor.

Supplementary Tables

Table S1 The amount of transition metals loaded on the Cu2O-based samples determined by ICPOES.

	Cu2O-	Cu2O-		Cu2O-111-3% TMs		Cu2O-	Cu2O-
Samples	100-3%	111-1%				111-5%	111-7%
	Ir	Ir	Co	Rh	Ir	Ir	Ir
Metal
content	2.79	0.98	2.85	2.80	2.89	4.86	6.82
(wt.%)

Table S2. The AQE for photocatalytic N2 fixation in recent reports.

Catalysts	AQE	Ref.
Cu2O-111-Ir	0.067% at 350 nm	Our work
ZnO@NC-Ni2	0.081% at 350 nm	ACS Catal. 2023, 13, 3242-3253
TiO2/Au/a-TiO2	0.005% at 254 nm	Angew. Chem. Int. Ed. 2018, 57, 5278-5282
Fe2O3@TixOy-Pz	0.032% at 365 nm	ACS Sustainable Chem. Eng. 2021, 9, 15331-15343
m-PCN-V	0.10% at 500 nm	ACS Appl. Energy Mater. 2018, 1, 4169-4177
CuCr-LDH	0.44% at 380 nm	Adv. Mater. 2017, 29, 1703828
6% Cu-TiO2	0.74% at 380 nm	Adv. Mater. 2019, 31, 1806482

Table S3 Performance comparison of various photocatalysts for N2 reduction.

	Catalysts	Catalysts	Catalysts	Catalysts	Reaction medium	Scavenger	Light source	Detection Method	Ammonia generation rate (μg gcat.-1 h-1)	Ref.
Cu2O-111-Ir					H2O	No	Full-spectrum	IC	173.8	Our work
										ACS Sustain.
TiO2			(P25)		H2O	No	Full-spectrum	IC	27	Chem. Eng. 2018, 6, 5342–
										5348.
										Appl. Catal., B
Ti3C2		MXene-P25			H2O	No	Full-spectrum	IC	193.32	2020, 273,
										119054.
JRC-TiO-6					H2O, 38℃	2-PrOH	λ > 280 nm	IC	62	J. Am. Chem. Soc. 2017, 139, 10929–10936.
Ru quantum dots/g-C3N4					H2O	No	780 nm > λ > 420	Indophenol blue method	184.14	Appl. Catal., A 2021, 617, 118112.
ZnO@NC-Ni2					H2O	No	Full-spectrum	Indophenol blue method	70.3	ACS Catal. 2023, 13, 3242−3253.
										ACS Sustain.
SA	Ru/TiO2-NS				H2O	CH3OH	Full-spectrum	Indophenol blue method	56.34	Chem. Eng. 2019, 7, 6813–
										6820.
	Ti-MOF				H2O (l)	No	λ > 400 nm	Indophenol blue method and IC	221.40	Appl. Catal., B 2020, 267, 118686.
										Angew. Chem.
Ru1/d-UiO-66					H2O (l)	No	Full-spectrum	Nessler’s reagent method and IC	959.04	Int. Ed. 2024, 63.2,
										e202314408.
PMo10V2@MIL- 88A					H2O (l)	No	Full-spectrum	IC	914.76	ACS Catal. 2023, 13, 7189−7198.
										J. Am. Chem.
Au	NBP/Rh			SSs	H2O (l)	No	λ > 420	IC	2487.6	Soc. 2024, 146,
										7734−7742.

Supplementary Methods

Materials. Copper chloride dihydrate (CuCl2·2H2O) and copper acetate anhydrous (Cu(CH3COO)2) were bought from Aladdin Chemical Company. Cobalt (II) chloride (CoCl2), Rhodium (III) chloride (RhCl3), Irdium (III) chloride (IrCl3), sodium hydroxide (NaOH), ascorbic acid (C6H8O6) and anhydrous glucose (C6H12O6) were obtained from Sigma-Aldrich Chemical Company. All chemicals were of analysis purity (AR) and utilized without further purification, and the water

(18.2 M Ω cm) utilized was generated by the ultrapure water system (Aike Water Treatment

Solution Provider, China).

Apparatus. The X-ray diffractometer (XRD) patterns were recorded on a Philips X’pert PRO X- ray diffractometer via Cu Ka radiation. The morphologies and element compositions were investigated via scanning electron microscopy (SEM, FEI-30 ESEM) and transmission electron microscopy (TEM, Hitachi H-7700). The ultraviolet visible diffuse reflectance spectroscopy (UVDRS) was obtained by an ultraviolet visible spectrometer (Hitachi UV-3900) in the scanning range of 200-800 nm. The PL spectra was collected by a FLS1000 fluorescence spectrophotometer (Edinburgh Instruments, UK). The photochemical reactor was installed to CEL-GPPCL system (Beijing China Education Au-light Co., Ltd.) equipped with a 300-W Xe lamp. The N2 temperature programmed desorption (N2-TPD) experimets (Micromeritics Auto Chem II) was employed to analyze the chemisorbed N2 over various samples. The ion chromatography (CIC-D120, Qingdao Shine, Co. Ltd.) was used to determine the concentrations of NH3 (as NH4[+] ) in each aliquot. The

contents of loaded matal clusters on Cu2O were determined by inductively coupled plasma optical emission spectrometer (ICP-OES, PerkinElmer).

Preparation of Cu2O-100. The Cu2O-100 was prepared according to the previous reports with minor modification.[S1] Briefly, 10 mL of NaOH solution (2.0 M) was added to CuCl2·2H2O aqueous solution (0.01 M, 100 mL) and stirred for 30 min. Next, the ascorbic acid solution added into the above mixture and continue stirring for 3 h. All the above experimental procedures were performed

under a water bath at 55°C. Subsequently, the brick red precipitates were centrifuged and washed with deionized water for several times. Finally, the Cu2O-111 was obtained after 12 hours vacuum drying at 60 ℃.

Synthesis of Cu2O-111. The Cu2O-111 were synthesized according to previously reported approach.[S2] Firstly, 2.995 g of Cu(CH3COO)2 was added into 20 mL deionized water and stirred continuously in a three-necked flask of 50 mL. Next, 10 mL of NaOH solution (12.5 M) was added drop by drop, heated the solution to 70 ℃ and lasted for 5 min. Subsequently, continue to add 0.58 g of glucose, and the mixture will gradually change from black to deep red. The reaction was maintained at 70 °C for 1 h and then cooled naturally to room temperature. Finally, the as-collected sample was washed with deionized water for several times and vacuum dried at 60 ℃ for 12 h.

Preparation of Ir clusters modified Cu2O catalyst. The preparation of Ir clusters modified Cu2O catalyst were synthesized through a NaBH4 reduction method. Typically, Cu2O-100 cube or Cu2O-

111 octa (50 mg) was dispersed in 25 mL deionized water and mixed with certain amount of IrCl3

with different mass ratios (Cu2O-100/111-x% Ir, x = 0, 1, 3, 5 and 7, respectively). After vigorous stirring for 30 min, the fresh NaBH4 solution (0.01 M, 10 mL) was added drop by drop and continue stirred at room temperature for 30 min. Next, the resulting materials were washed with deionized water for four times, the as-constructed Cu2O-100-Ir and Cu2O-111-Ir samples were obtained after 12 h vacuum drying at 60 ℃. Other metal clusters including Co, and Rh modified Cu2O samples with a mass ratio of 3% were prepared by a similar manner except that IrCl3 was replaced with CoCl2 and RhCl3 respectively. In addition, the composition of Cu2O-100/111-x% Ir and other metal clusters loaded on Cu2O with a mass ratio of 3% were determined by the ICP-OES (Table S1), which is basically consistent with the desired loading level.

Screening and optimization of Cu2O-based photocatalysts. To achieve an excellent N2photofixation performance, the ion chromatography was employed to assess the content of NH3 generation (Figure S1). Firstly, the photocatalytic NRR activities of Cu2O with different exposed crystal facets (i.e., Cu2O-100 and Cu2O-111) were investigated. As shown in Figure S2, with the increase of photoreaction time, the Cu2O-111 catalyst exhibits a better NRR activity than Cu2O100. Next, the content of Ir clusters loaded on Cu2O-111 was further optimized. From Figure S3, it can be seen that the productivity of synthesized NH3 varies with the change of Ir content. Notably, these different Ir-loading Cu2O-100 catalysts display volcanic activity at each photoreaction time node, as well as the synthesis of NH3 on the Cu2O-11-2.89% Ir sample possesses the highest yield. Then, the NH3 yield of Cu2O-111-2.85% Co and Cu2O-111-2.80% Rh with the same loading ratio was also compared (Figure S4). As shown in Figure S4, the Cu2O-111-

2.89% Ir catalyst also exhibits the optimal NRR activity, manifesting that the Ir clusters has the most favorable promotion effect on the dominant {111} crystal plane of Cu2O. For the sake of simplicity, the Cu2O-111-2.85% Co, Cu2O-111-2.80% Rh and Cu2O-111-2.89% Ir was respective shortened to Cu2O-111-Co, Cu2O-111-Rh and Cu2O-111-Ir and conducted for the subsequent characterization and experiments.

Photocatalytic nitrogen fixation

The photocatalytic synthesis of NH3 experiment was carried out in photocatalytic N2-fixation reactor as shown in Figure S24. The photocatalytic N2 fixation is achieved on the three-phase interface, including N2 in the gas, H2O in the liquid and the catalyst in the solid phase. Synthetic ammonia performance experiments were conducted at room temperature and atmospheric pressure. A 300 W Xe lamp (Full-spectrum) was used as light source and 10 cm away from the light source to the liquid surface. Firstly, 20 mg photocatalyst were dispersed in 50 mL deionized water in a cell equipped with water circulation. Secondly, the mixture was continuously stirred in the dark with high-purity N2 bubbled at a flow rate of 200 mL·min[-1] for 30 min, then turn on the light and 4.0 mL of reaction solution was taken out from the reaction vessel in every 30 min. The reaction mixture was purified by removing the photocatalyst by using the 0.22 μm filter. The obtained solution was further analyzed by an ion chromatography (CIC-D120, Qingdao Shine, Co. Ltd.).

N2 temperature-programmed desorption

100 mg of catalyst was placed at the bottom of the U-shaped quartz tube and preheated in Ar flow (50 mL min[-1] ) at 300 °C for 0.5 h and then cooled down to 25 °C. After pretreatment, the feeding N2 flowed through the catalyst bed at 25 °C for 1 h. Then, the physisorption of N2 was removed by Ar flow (50 mL min[-1] ) at 50 °C for 0.8 h. Finally, the catalyst bed was heated from 50 °C to 600 °C at 10 °C min[-1] . We monitored a wide range of desorbing species to identify the main products that are generated from reactions of N2 on catalyst and found that the only species desorbed from the N2-exposed samples is N2, as analyzed on-line with a mass detector.

Determination of apparent quantum efficiency (AQE)

The catalytic experiments for determining AQE were performed in 50 mL pure water, and the irradiation area was 12.56 cm[2] . And 20 mg of Cu2O-111-Ir was used as the photocatalyst. To obtain the AQE, the light was filtered by different monochromatic filters (i.e., 350, 500 and 600 nm), and the reaction time was 1 h. The light intensities were measured to be 50.2, 39.6 and 42.7 mW cm[-2] , respectively. The AQE was calculated through the following equation:

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where Ne , Np and NAM represent the number of reacted electrons, incident photons and generated ammonia, respectively; nAM represents the molar number of generated ammonia; ν , W , A and t are the incident light frequency, intensity, irradiation area and time, respectively; NA and h are the Avogadro’s constant (6.02 × 10[23] mol[-1] ) and Planck constant (6.626 × 10[-34] J·s), respectively. As is known to us, the value of NA and h is 6.02 × 10[23] mol[-1] and 6.626 × 10[-34] J·s, respectively.

Determination of hydrazine (N2H4)

The hydrazine presented in the photocatalytic reaction solution was estimated by the method of Watt and Chrisp with some modification,[S3-S5] which contains the following steps: ( ⅰ ) 2.0 mL

post-pNRR solution was collected from photochemical reactor with further removal of the photocatalyst by using the 0.22 μm filter. ( ⅱ ) 2.0 mL of color agent was added into post-pNRR solution. The color reagent solution consists of 5.99 g of para-(dimethylamino) benzaldehyde, 30 mL of HCl, and 300 mL ethanol. After reacting in a dark condition at room temperature for 20 min, the sample absorbance was investigated by UV-vis spectroscopy (UV-17800, Shimadzu). The correction curve was successfully established for N2H4 with various concentrations.

In-situ Fourier-transform infrared spectroscopy experiments

In-situ Fourier-transform infrared spectroscopy (FTIR) was performed by adopting a Nicolet-iS50 Fourier-transform infrared spectrometer, equipped with a Harrick Scientific in-situ cell and a mercury-cadmium-telluride (MCT) detector cooled by liquid N2. The sample (20 mg) was pressed into thin slices by a hydraulic machine and placed in the in-situ cell. Then, the system was evacuated to an internal pressure of 10[-4] mbar and heated at 200 ℃ for 60 min with a heating rate of 8.5 ℃ min[-1] . When the temperature was cooled to 30 ℃, the molecular pump was closed and then the background was tested. After that, pure N2 with H2O vapor was pumped into the in-situ cell. At the same time, turn on the light to drive the reaction and test the IR signal at different time intervals.

Density functional theory simulations

The density functional theory computations were carried out by the CASTEP code,

employing the ultrasoft pseudopotential.[S6-S8] The exchange correlation potential was represented by the Perdew-Burke-Ernzerhof (PBE) functional within the generalized gradient approximation (GGA).[S9] A 3 × 3 ×1 supercell Cu2O (111) surface with nine atomic layers was established (with 108 Cu and 54 O atoms). Meanwhile, a 4 × 4 ×1 supercell Cu2O (100) surface with eight atomic layers was established (with 128 Cu and 64 O atoms). Periodic boundary conditions were employed along x and y directions with a vacuum region of 15 Å. During the optimization process, the bottom three layers of atoms are fixed and the other layers are relaxed. The cutoff energy for the plane-wave-basis expansion is set to be 450 eV, and the convergence tolerances of energy, force and maximum displacement are set to 1.0  10[-5] eV/atom, 3.0  10[-2] eV/Å and 1.0  10[-3] Å, respectively. The k-points grid sampling of Monkhorst-Pack scheme was set as 2 × 2 × 1 in the irreducible Brillouin zone. The Hubbard U correction is used to describe the Coulomb electron interaction precisely, and the U value of Cu and O are set to 11 and 7.5 eV, respectively, is consistent with previous work.[S10-S12] Meanwhile, the DFT-D correction method is used to describe the long-range van der Waals interaction.[S13]

The adsorption energy ( E ab) of N2 were defined as:

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E (sub+N2) and E (sub) are the total energy of the Cu2O substrates with and without N2, respectively. E (N2) is the total energy of N2 molecules. The Gibbs free energy change (ΔG) of the elementary step was calculated by:

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Where ∆ E is the total energy difference, Δ E ZPE is the change in the zero-point energy and the entropy, T is the temperature ( T = 298.15 K), and Δ S is the entropy change.

Supplementary References

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- Palladium-modified cuprous(i) oxide with {100} facets for photocatalytic CO2 reduction. −
- Nanoscale 2021, 13, 2883 2890.
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methane formation from CO2. ACS Catal. 2022, 12, 4526 4533.
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S4. Zhao, J. X.; Liu, X. J.; Ren, X.; Sun, X.; Tian, D. X.; Wei, Q.; Wu, D. Defect-rich ZnS nanoparticles supported on reduced graphene oxide for high-efficiency ambient N2-to-NH3 conversion. Appl. Catal., B 2021, 284, 119746.
S5. Qiu, W. B.; Xie, X.-Y.; Qiu, J. D.; Fang, W.-H.; Liang, R. P.; Ren, X.; Ji, X. Q.; Cui, G. W.; Asiri, A. M.; Cui, G. L.; Tang, B.; Sun, X. P. High-performance artificial nitrogen fixation at ambient conditions using a metal-free electrocatalyst. Nat. Commun. 2018, 9, 3485.
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S11. Gupta, D.; Meher, S. R.; Illyaskutty, N.; Alex, Z. C. Facile synthesis of Cu2O and CuO nanoparticles and study of their structural, optical and electronic properties. J. Alloy. Compd. 2018, 743, 737−745.
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