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Article
Salt aqua regia as a green solvent for
recovering precious metals
Anting Ding, Ming Li, Chuanying
Liu, Xingwang Zhang, Lecheng
Lei, Chengliang Xiao

xiaoc@zju.edu.cn

Highlights
An alternative solvent to aqua
regia can recover precious metals
from spent catalyst

A photovoltaic effect has been

found in salt aqua regia on
oxidative dissolution

Potential to replace aqua regia in

hydrometallurgical processes

Excellent electrochemical stability

and electrical conductivity for
electrodeposition

In this work, Ding et al. report a solvent dubbed ‘‘salt aqua regia’’ prepared by
mixing Al(NO3)3$9H2O and NaCl in aqueous solution. Precious metals such as Pd
and Au completely dissolve in it and can be recovered with leaching and one-step
electrodeposition.

Ding et al., Cell Reports Physical Science 3,

101159
December 21, 2022 ª 2022 The Author(s).
https://doi.org/10.1016/j.xcrp.2022.101159
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Article
Salt aqua regia as a green solvent
for recovering precious metals
Anting Ding,1,2,3 Ming Li,2,3 Chuanying Liu,2 Xingwang Zhang,1,2 Lecheng Lei,1,2
and Chengliang Xiao1,2,4,*

SUMMARY
Spent catalysts are valuable secondary resources of precious
metals. Traditional methods of recovering precious metals typically
use highly corrosive aqua regia, which is extremely dangerous
and leads to severe environmental pollution. Here, we report an
alternative route to recover precious metals from spent catalysts us-
ing purely inorganic salt solutions consisting of Al(NO3)3$9H2O and
NaCl, which we name ‘‘salt aqua regia.’’ The precious metals palla-
dium and gold can be completely dissolved in it. In simulated and
real recovery processes, high-purity palladium and gold products
are obtained through leaching and one-step electrodeposition.
The solvent keeps almost the same dissolution properties and elec-
trochemical stability even after three cycles. As salt aqua regia is
safe and non-volatile and has good solubility for precious metals
and electrochemical stability, it has excellent prospects for applica-
tion in precious metals recovery.

INTRODUCTION
Due to their unique physical and chemical characteristics, such as strong catalytic ac-
tivity, electrical conductivity, and corrosion resistance,1–3 precious metals are essen-
tial to the world economy and are widely used in a wide range of industrial products
and processes, such as modern industrial catalysts4–6 and electronic devices.7–9

However, due to the continuous reduction of raw ore and rapidly rising demand,
these precious metals have been classified as rare resources by international orga-
nizations.2,10 The demand for precious metals is rising because of the expansion
of industries utilizing their products, which results in the global supply shortage.11,12
Recovery of precious metals from secondary resources is an effective method of
lowering supply risk given the fragile nature of the precious metals supply
chain.13–15 End-of-life products are being produced quickly and are becoming a
substantial source of precious metals. Since they make up more than 90% of the
precious metals used in industry, spent catalysts and electronic waste are the ones
that should raise the most concern.1,16–28 These two resources have developed
1College of Chemical and Biological
into a lucrative ‘‘urban mineral.’’29–31
Engineering, Zhejiang University, Hangzhou
310058, China
Due to the insoluble nature of precious metals, extracting them from secondary 2Institute
of Zhejiang University-Quzhou, Quzhou
sources remains challenging.11 It is frequently necessary to dissolve precious metals 324000, China
in strongly oxidizing circumstances. Aqua regia, a mixture of concentrated nitric acid 3These authors contributed equally
and hydrochloric acid in a volume ratio of 1:3, is the most commonly used solvent in 4Lead contact
the industry. Its use raises environmental and security problems because it is highly *Correspondence: xiaoc@zju.edu.cn
poisonous and corrosive.32 https://doi.org/10.1016/j.xcrp.2022.101159

Cell Reports Physical Science 3, 101159, December 21, 2022 ª 2022 The Author(s). 1
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
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Scientists have developed a variety of different solvents to replace aqua regia in the
process of recovering precious metals in order to address these issues. Lin et al.
created ‘‘organic aqua regia’’ to dissolve Pd, Au, and Ag by mixing SOCl2 with a po-
lar aprotic organic solvent such as pyridine, imidazole, or N, N-dimethylforma-
mide.33 Organic solvent acetonitrile with halogen and halide was also used to leach
Pd, Au, and Ag.34 However, neither organic solvent like SOCl2 nor halogen is consid-
ered an environmentally friendly chemical. These techniques pose a serious risk to
the environment due to the development of significant amounts of secondary waste
from these chemical agents and the release of hazardous exhausts.35 To enable the
dissolution of precious metals, numerous investigations have been devoted to the
development of an inorganic solution system with potent oxidizing and coordinating
properties, similar to aqua regia. Wang et al. replaced nitric acid with NaClO solu-
tion in the aqua regia, with 4M hydrochloric acid as a coordination agent to leach
Pt successfully.36 Ding et al. utilized the mixture of hydrochloric acid, FeCl3, and
NaCl to dissolve Pd.37 However, these processes consumed large amounts of inor-
ganic acids that could not be recycled, which produced vast quantities of waste-
water. Highly concentrated salt solutions, instead of inorganic acids, have been
applied to recover some metals from secondary resources. A mixture of
AlCl3$6H2O, Al(NO3)3$9H2O, and a small amount of water was used to recover
precious metals, and the dissolution of precious metals was achieved by Forte
et al.32 However, the leaching system was not a complete solution with amounts
of salts precipitated, and neither solution characterization nor dissolution mecha-
nism studies have been performed.

To solve this problem, we develop a highly concentrated salt solution formulated with
Al(NO3)3$9H2O and NaCl named salt aqua regia as a powerful green solvent to recover
precious metals, and precious metals Pd and Au are successfully recovered from spent
catalysts with salt aqua regia leaching and one-step electrodeposition.

RESULTS
Salt aqua regia as a powerful solvent
In this work, we choose the simplest salt, NaCl, combined with Al(NO3)3$9H2O in
aqueous solution to discover the new salt aqua regia system. For the five salt aqua
regia solutions with varied Al(NO3)3$9H2O to NaCl molar ratios, as shown in
Figure 1A, with the proportion of saturated NaCl solution increasing, the conductiv-
ity of salt aqua regia gradually increased, while the viscosity was the opposite. This
might be because the conductivity of saturated NaCl solution was more excellent
than molten Al(NO3)3$9H2O, while the viscosity was relatively smaller. Regardless
of the molar ratio of Al(NO3)3$9H2O to saturated NaCl solution in salt aqua regia,
compared with ionic liquids, it presented good electrical conductivity and low vis-
cosity.38 Figure 1B illustrates that the density gradually decreased as the saturated
NaCl fraction in salt aqua regia increased, and the density and NaCl fraction showed
a good linear relationship. The excellent linear relationship indicated no significant
gas release due to the violent reaction between Al(NO3)3$9H2O and NaCl solution.
The acidity of solutions has been determined using various techniques, including
infrared spectroscopy,39 13C nuclear magnetic resonance (NMR),40 and Hammett
acidity.41,42 It is common practice to utilize the Hammett acidity formula to assess
the acidity of an organic acid, inorganic acid, aqueous solution, and non-aqueous
solvent. This approach relies on the technique of UV-visible (UV-vis) spectrophotom-
etry, which has modest equipment needs, little workload, and good accuracy. The
UV-vis absorbance of ethanol, H2SO4, and five salt aqua regia solutions is listed in
Table S1. Hammett acidity of five salt aqua regia solutions was calculated using

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Figure 1. Solubility for precious metals and physical and chemical properties of salt aqua regia
(A–C) Electrical conductivity, viscosity, density, and Hammett acidity of five salt aqua regia.
(D) Dissolution ratios of Ag, Au, Pd, Pt, and Rh in salt aqua regia. The data points with error bars
were the average of two independent measurements.

Equations 5 and 6. As shown in Figure 1C, with the increase of the saturated NaCl
solution component in salt aqua regia, the values of Hammett acidity underwent a
process of first decreasing and then increasing, indicating that its acidity first
increased and then decreased. Hammett acidity reached the maximum when the
molar ratio of Al(NO3)3$9H2O and NaCl was 1:0.5. Hammett acidity experiments
showed that aqua regia was highly acidic and powerful. Concentrated salt solutions
have been applied to replace inorganic acids to recover rare earth elements from
waste NdFeB.43 The presence of nitrate ions in aqueous salt solutions enhances
the oxidizing properties of the solution. It provides the possibility for aqueous salt
to dissolve precious metals. The physical data of electrical conductivity, viscosity,
density, and Hammett acidity of five salt aqua regia are listed in Table S2.

Ag, Au, Pd, Pt, and Rh are five common precious metals in electronic circuits and catalysts.
These five precious metals were leached in salt aqua regia to see their solubility. 5 g salt
aqua regia (the molar ratio of Al(NO3)3$9H2O and NaCl was 1:0.5, with the maximal Ham-
mett acidity) and 0.1 g precious metals were mixed together for 300 min under 80
C. As
shown in Figure 1A, Au and Pd could quickly be dissolved in salt aqua regia, while the ex-
tra three precious metals could not be dissolved. 98.21% G 2.37% of Au and 97.18% G
3.22% of Pd were dissolved in salt aqua regia in 300 min. Ag was insoluble in salt aqua
regia because the large amounts of chloride ions in the solution reacted with Ag+ to
form AgCl precipitates once it was dissolved, thus preventing further dissolution.44
Therefore, Ag was insoluble in salt aqua regia. For Pt and Rh, it might be that the solvency
capacity of salt aqua regia was insufficient to dissolve these two precious metals at 80
C
and atmospheric pressure. Just like Ru, Rh, and Ir, they could only be dissolved by aqua
regia at high temperature and pressure but not at room temperature and pressure.45
With good solubility toward Pd and Au, good electrical conductivity, and low viscosity,

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Figure 2. Dissolution ratios of Pd and Au under different conditions

(A–D) Effect of Al(NO 3 ) 3 $9H 2 O/NaCl, liquid to ratio, time, and different nitrate on the dissolution
ratios of Pd and Au. The data points with error bars were the average of two independent
measurements.

salt aqua regia facilitated its application of precious metals leaching in practical produc-
tion, reducing production costs and also providing the possibility of subsequent electro-
chemical methods to recover dissolved precious metals.

Leaching experiments
As initial tests indicated, the salt aqua regia solution could dissolve precious metals Pd
and Au. In this section, the operating factors, including Al(NO3)3$9H2O to NaCl molar ra-
tio, liquid-to-solid ratio, leaching time, NaCl with different nitrate species, and
Al(NO3)3$9H2O with different chloride salt species, were investigated to determine the
optimal conditions.

As shown in Figure 2A, with an increasing Al(NO3)3$9H2O to NaCl molar ratio, the
dissolution ratios of Pd and Au underwent an upward and then downward process.
When the ratio of Al(NO3)3$9H2O to NaCl was 1:0.5, the dissolution ratio of Pd
reached 96.13% G 3.32%, while for Au, the maximum dissolution ratio appeared
in the ratio of 1:1, under which the salt aqua regia dissolves 99.82% G 3.22% of
Au in 3 h. The composition difference of the salt aqua regia, which was highly selec-
tive for Pd and Au dissolution, might be due to differences in the ligand patterns re-
sulting from differences in the ionic valence states of the two metals after dissolution.

In Figure 2B, when the liquid to solid ratio reached 100:1 and 50:1, almost 100% of
the Pd and Au were dissolved. The dissolution ratio of Pd and Au gradually
decreased when decreasing the liquid to solid ratio. Nevertheless, the solubility of
Pd and Au in salt aqua regia did increase gradually with the decrease of the
liquid-to-solid ratio. When the liquid-to-solid ratio was 20:1, the solubility of Pd
reached 64,183 G 2,647 ppm. Compared with Pd, the solubility of Au was a little
lower, reaching 50,608.9 G 2,346.8 ppm. Considering the dissolution ratio and

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Figure 3. Dissolution mechanism

(A) UV-vis spectra of [PdCl 4 ] 2, Pd(II) in salt aqua regia solution, and [Pd(NO 3 ) 4 ] 2.
(B and C) Raman spectra and cyclic voltammograms of Pd(II) in salt aqua regia solution.
(D) The evolution process of free radical OH in the dissolution reaction using EPR.

solubility, the optimal liquid-to-solid ratio of Pd and Au was 50:1. As shown in Fig-
ure 2C, the dissolution reactions of Pd and Au reached equilibrium at approximately
180 min, and almost 100% of Pd and Au could be dissolved, so 180 min was the
optimal time. Leaching experiments of Pd and Au were carried out with different ni-
trates paired with NaCl. As can be seen from Figure 2D, except for Fe(NO3)3$9H2O
and Al(NO3)3$9H2O, the other nitrates with NaCl were almost entirely insoluble
for these two precious metals. It was probably because Zn(NO3)2$6H2O,
Mg(NO3)2$6H2O, and NaNO3 were too weak to ionize hydrogen ions in an aqueous
solution, and the solutions were not acidic enough to destroy the dense structure of
Pd and Au. Although the combination of Fe(NO3)3$9H2O and NaCl could also
dissolve Pd and Au, there were only 16.36% G 1.21% and 24.14% G 2.45% disso-
lution ratios of Pd and Au, respectively, which are much lower than the combination
of Al(NO3)3$9H2O and NaCl. Therefore, the most optimal nitrate was
Al(NO3)3$9H2O. At the same time, Al(NO3)3$9H2O with different chloride salt formu-
lated solutions was also leached for Pd and Au. As seen in Figure S1, the difference in
dissolution ratio between the different chloride salts was not as significant as that of
the different nitrates paired with NaCl in the previous experiment. All five chloride
salts showed good dissolution results. It might be seen that the chloride salts in
the salt aqua regia could be replaced, but since NaCl was the most economical
and widely available, we chose NaCl as the chloride salt component in the salt
aqua regia. Dissolution ratios of Pd and Au under different conditions are listed in
Tables S3 and S4.

Dissolution mechanism
In order to figure out the mechanism of the dissolution reaction, UV-vis spectros-
copy analysis was applied. Numerous studies have been conducted on the chem-
ical forms of Pd in acidic and aqueous media from both scientific and industrial

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Figure 4. Overall recovery process

(A) Plot of reduction peak current and square root of sweep speed at 353, 358, and 363 K.
(B) Curve of current variation with time during constant potential deposition.
(C) PXRD pattern of recycled Pd.
(D) Dissolution ratio and recovery efficiency of Pd(II) with three cycles. The data points with error
bars were the average of two independent measurements.

perspectives. Previous studies implied that in aqueous acidic solutions of Pd(II)

containing Cl or NO3, Pd(II) was likely to create a square-planar structure coor-
dinated with four ligands of Cl, NO3, and water.46–50 Figure 3A shows that in
[PdCl4]2 and salt aqua regia containing Pd(II) solutions, firm absorption peaks
at 207 and 237 nm and weak absorption peaks at 312 nm mainly corresponded
to [PdCl4]2 octahedron.51 In Pd(NO3)2$2H2O solution, two peaks were, respec-
tively, observed at 288 and 381 nm, which correspond to [Pd(NO3)4]2.52 These
two peaks have not appeared in salt aqua regia containing Pd(II) solutions, so it
could be inferred that in salt aqua regia, Pd(II) only coordinated with chloride
ions instead of nitrate. To verify this hypothesis, Raman spectroscopy analysis
was carried out on Pd(II)-loaded salt aqua regia. As shown in Figure 3B, three
bands of 164, 275, and 303 cm1 were observed and mainly correspond to
[PdCl4]2.53 Figure 3C showed the cyclic voltammetry curves at 353 K for the
salt aqua regia containing Pd(II). Only one reduction peak at about 0.9 V versus
saturated calomel electrode (SCE) was observed on the curve. It could also be in-
ferred that there was only one coordination mode of Pd(II) in salt aqua regia.
Combining UV-vis and Raman tests, it could be concluded that Pd(II) was coordi-
nated with Cl in salt aqua regia. It is acknowledged that the precious metals
leaching system should contain the coordination agent and the oxidizing agent.36
The active species is the key factor for oxidizing zero-valent precious metals to its
positive value. Through the signal peak of electron paramagnetic resonance (EPR)
spectroscopy, it was found that the concentration of $OH and $O2 in the solution
increased as the reaction proceeded (Figures 3D and S2). It has been proven
through capture experiments that light and OH are the critical elements in the
dissolution reaction (Figure S3). Charge separation under illumination and the
photovoltaic effect have been found in an ionic liquid solution.54 The composition
of salt aqua regia is very similar to that of ionic liquids. So, the photovoltaic effect

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Figure 5. The flowchart of the recovery process

Recovery process of Pd and Au with salt aqua regia leaching and one-step electrodeposition. The used salt aqua regia is recycled three times.

could also be applied to it. NO2 was detected in the ion chromatogram measure-
ments (Figure S4). So, there might be two ways to generate $OH:55

salt aqua regia/e  + h + ðhvÞ h + + H2 O/OH + H + ; and (Equation 1)

NO2  /NO + O  ðhvÞ O  + H + /OH : (Equation 2)

Diffusion coefficient of Pd(II) in system

The diffusion coefficients of Pd(II) in the salt aqua regia system were obtained from the
cyclic voltammetry curves of the Pd-containing salt aqua regia at different tempera-
tures of 353, 358, and 363 K. Electrochemical test data at different scan rates under
three temperatures are listed in Tables S5–S7. Calculated by Equation 8, the diffusion
coefficient for 358 K was 6.51 3 105 cm2/s. As shown in Figure 4A, with the increase of
temperature, the diffusion coefficient increased to 1.98 3 104 cm2/s at 368 K, indi-
cating that the diffusion rates of Pd(II) in salt aqua regia became faster. The diffusion
coefficients of Pd(II) in ionic liquids were in the order of 107.54 Therefore, the diffusion
coefficients of Pd(II) in salt aqua regia were 2–3 orders of magnitude higher than that of
ordinary ionic liquids. This offered considerable prospects for the direct recovery of
precious metals from salt aqua regia by electrodeposition.

Overall recovery process

The Pd wire was first leached out with the salt aqua regia to obtain a simulated so-
lution for Pd recovery. Afterward, after 15,000 s of electrodeposition at 0.9 V versus
SCE, the color of the salt aqua regia containing Pd(II) slowly changed from dark
brown to light brown, indicating that the concentration of Pd(II) was gradually
decreasing. Figure 4B showed the current density curve with electrolysis time in
the cycle 0 experiment. After 1 h of leaching, the concentration of Pd(II) was
49.6 mM, indicating that the dissolution ratio was 99.2%. The final concentration
of Pd(II) was 1.3 mM after 15,000 s of electrodeposition, showing that the recovery

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efficiency of electrodeposition was 97.4%. Current efficiency was also calculated by

Equation 10, and it reached 83.1%.

The diffraction peaks of the produced Pd product, as shown in Figure 4C, were in
good agreement with the accepted Pd X-ray diffraction (XRD) patterns (Joint
Committee on Powder Diffraction Standards [JCPDS] card number 46-1043]. En-
ergy-dispersive X-ray spectroscopy (EDS) spectrum of Pd in Figure S10 revealed
that it was nearly 100% pure (the elemental composition is listed in Table S8). As
shown in Figure 4D, after three cycles, the dissolution ratio of Pd by salt aqua regia
and the electrodeposition recovery of Pd decreased little and retained quite an
excellent performance. The current efficiency dropped a bit after each cycle, most
likely due to the concomitant production of other electrolytic reactions, such as
the electrolysis of water to produce hydrogen and oxygen. The dissolution ratio,
electrodeposition recovery, and current efficiency are listed in Table S9.

The simulated recovery process of the Au was very similar to that of Pd, but constant
current electrodeposition was applied in the recovery process. 98.2% G 2.6% of Au
was dissolved, and 92.1% G 2.3% of Au was recovered, with 10 h at 40 mA cm2
(cathodic). The current efficiency of Au was a bit lower than that of Pd and reached
48.6% G 1.5%. Both powder XRD (PXRD) patterns and EDS spectra of recycled Au
(Figures S13 and S14) showed that the Au product was of high purity (the elemental
composition is listed in Table S10) As listed in Table S11, the dissolution ratio, elec-
trodeposition recovery, and current efficiency dropped slightly but remained almost
the same level after three cycles. The flowchart of the Pd and Au recovery process
using salt aqua regia with one-step electrodeposition is given in Figure 5.

Recovery of precious metals from spent catalysts

After the leaching of the salt aqua regia, the dissolution ratios of the various metals in
the spent catalyst other than Al (the salt aqua regia itself contains a large amount
of Al) were calculated. The leachate of the Pd catalyst and the Au catalyst were sepa-
rately electrodeposited for 30 min at 26.67 mA cm2 (cathodic) using a three-elec-
trode system with constant current. After the product was obtained on the
electrodes, the product was microwave digested along with the working electrodes.
The product content and the remaining electrolyte were measured by inductively
coupled plasma mass spectrometry (ICP-MS) to calculate the electrodeposition re-
covery. The mass composition, dissolution ratio, and recovery efficiency of metals
in the Pd and Au catalyst are listed in Tables S12 and S13, respectively. In the Pd
catalyst, 98.92% G 1.11% of Pd was dissolved, and the recovery efficiency reached
70.1% G 3.33%. 0.02% G 0.0005% of Pt was dissolved, mainly due to the extremely
high liquid-to-Pt ratio (>9 3 104). However, no Pt was detected on the electrode,
ensuring the purity of Pd product. For the Au catalyst, the dissolution ratio was
98.88% G 1.01%, and 72.5% G 2.22% of Au was recovered.

DISCUSSION
In this work, a powerful green solvent of salt aqua regia was developed on the com-
bination of Al(NO3)3$9H2O and NaCl. Precious metals in spent catalysts were suc-
cessfully recovered by salt aqua regia leaching with one-step electrodeposition.
The salt aqua regia leaching process is facile and requires simple equipment. The
raw material is easy to store and transport without the operational danger and corro-
siveness of strong acids. The leaching process is safe, and no volatile gases are
produced, owing to the stable and non-volatile qualities of salt aqua regia. The
green and efficient electrodeposition recovery of precious metals after leaching

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are due to the good electrical conductivity of the salt aqua regia and the high diffu-
sion coefficient of precious metal ion in it.

Precious metals have been traditionally recovered using strong inorganic acids or vol-
atile organic solvents, which had a considerable detrimental impact on the environment
regarding human survival, safe use of freshwater, global warming, and other issues. The
recovery of precious metals would be more environmentally friendly if strong inorganic
acids and volatile organic solvents were swapped out for the green solvent salt aqua re-
gia and if the process was optimized with one-step electrodeposition.

EXPERIMENTAL PROCEDURES
Resource availability
Lead contact
Further information and requests for resources should be directed to and will be ful-
filled by the lead contact, Chengliang Xiao (xiaoc@zju.edu.cn).

Materials availability
All materials generated in this study are available from the lead contact without
restriction.

Data and code availability

The datasets generated during this study are available from the lead contact upon
reasonable request.

Metal dissolution experiments

Salt aqua regia was prepared by mixing Al(NO3)3$9H2O and saturated NaCl solution
(mass ratio of NaCl to H2O was 0.384:1) with varied Al(NO3)3$9H2O to NaCl molar
ratios at 80
C. The melting point of Al(NO3)3$9H2O is 73.5
C, so the salt aqua regia
can be guaranteed to be in liquid form. In dissolving precious metals Au, Ag, Pd, Pt,
and Rh, 5 g salt aqua regia and 0.1 g metal wires were added into a 10 mL vial and
sealed carefully, and the molar ratio of Al(NO3)3$9H2O to NaCl was 1:0.5. The
mixture was stirred on a collecting thermostatic magnetic stirrer at 80
C for
300 min with a stirring speed of 500 RPM. After dissolution, the liquid and undis-
solved solids were separated by a 10 mL syringe and a filter head. The liquid was
diluted using 1 M HNO3, and the concentrations of precious metals were analyzed
by ICP-MS. In the leaching tests of Pd and Au, the temperature adopted in the ex-
periments was 80
C, the leaching time was 180 min, and the stirring speed was
500 RPM except for the respective condition experiments.

The dissolution ratio (D) of the metals were calculated using the following equation:


D = wM;d $mSAR mM;r $100%; (Equation 3)

where wM,d denotes the mass concentration of metal in salt aqua regia solutions,
mSAR denotes the mass of salt aqua regia solutions after dissolving, and mM,r de-
notes the metal quality in metal wires before dissolution.

Experiments on the physical and chemical properties

The conductivity and viscosity of five salt aqua regia with different Al(NO3)3$9H2O to
NaCl molar ratios (Al(NO3)3$9H2O:NaCl = 1:0.2, 1:0.5, 1:0.8, 1:1, 1:2) were
measured under 80
C by a conductivity meter and a rotary viscometer, respectively.
Moreover, these five solutions were poured into a volumetric flask, and the volume
was adjusted to 10 mL. The density of the solutions was calculated from the mass to
volume ratios. UV-vis was used to analyze the Hammett acidity of five salt aqua regia

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solutions. Indicator 4-nitroaniline (pKBH+ = 0.99, peak wavelength at 377.5 nm43) was
dissolved at a concentration of 8.5 mg/L in ethanol (to make an all-alkali-type solu-
tion), 98% H2SO4 (to prepare an all-proton-type solution), and five salt aqua regia
solutions. Following complete mixing, the solutions were left to sit at room temper-
ature in the dark for 2 h before UV-vis measured the absorbance of 4-nitroaniline.
Proton transfer reaction occurs in the solution between indicator basic type B and
its conjugated acid (proton type BH+):

B + H + 4BH + : (Equation 4)
Ion balance defines Hammett acidity as follows:

H0 = pKBH +  IgðCBH + Þ=CB Þ; (Equation 5)

where KBH+ is the ion equilibrium constant of 4-nitroaniline (0.99), and the indicator’s
proton-type concentration to its base-type concentration is expressed as CBH+/CB.
According to Lambert-Beer law, CBH+/CB at a fixed wavelength is as follows:
 
 l 
CBH + =CB = AlB  Al A  AlBH + ; (Equation 6)

where ABl is the indicator’s all-alkali-type absorbance of the same concentration at a

fixed wavelength degree, ABH+l is its all-proton-type absorption of the same con-
centration at the same wavelength degree, and Al is the indicator’s absorbance in
the medium being measured at the same conditions as ABl and ABH+l.

Raman measurements
Raman spectra were applied to analyze complex in Pd(II) containing salt aqua regia
solution. 5 g salt aqua regia solution dissolving Pd wire with a liquid-to-solid ratio of
50:1 was stirred on a collecting thermostatic magnetic stirrer at 80
C for 300 min with
a stirring speed of 500 RPM.

EPR and IC measurements

In EPR and IC experiments, the salt aqua regia solution (molar ratio of Al(NO3)3$9H2O
to NaCl was 1:0.5) was diluted with water until it doubled in volume so that the system
could remain in liquid form at room temperature (EPR and IC measurements could only
be conducted at room temperature). The signals of free radicals and ions over time af-
ter the solution been prepared were detected separately.

Cyclic voltammetry curve

The cyclic voltammetry curves of the Pd(II) and Au(III) in salt aqua regia were investigated
by the electrochemical workstation (CHI760, Chen Hua, Shanghai, China) connected to a
three-electrode system. The working and counter electrodes were both Pt chips
(0.75 cm2 for working electrode and 1.50 cm2 for counter electrode), and the SCE was
the quasi-reference electrode. For the preparation of analysis solutions, 0.2128 g Pd
or 0.3940 g Au wires were dissolved for 1 h in 40 mL salt aqua regia whose molar ratio
of Al(NO3)3$9H2O to NaCl was 1:0.5 and 1:1, and the concentration of Pd (II) and
Au(III) were 50 mmol/L when fully dissolved, respectively. Cyclic voltammetry
curves were obtained with scanning speeds of 0.02, 0.04, 0.06, 0.08, and 0.10 V/s under
353 K.

Light and radical scavenging test

The dissolving object was 50 mg Pd wire leaching in salt aqua regia whose molar ratio
of Al(NO3)3$9H2O to NaCl was 1:0.5 with a 1:50 solid-to-liquid ratio. For capturing
light, the reaction process was carried out under complete shade. For capturing the
free radicals, 5 mg scavenger was introduced to the process, and only one type of
free radical could be collected in one experiment. Electrons (e), holes (h+), superoxide

10 Cell Reports Physical Science 3, 101159, December 21, 2022

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radicals ($O2), and hydroxyl radicals ($OH) were captured by potassium dichromate,
EDTA-2Na, p-benzoquinone, and tertiary butyl alcohol, respectively.

Diffusion coefficient test experiment

Cyclic voltammetry curves were also conducted at 358 and 363 K for the Pd(II) in salt
aqua regia solution. The electrochemical reduction reaction of Pd(II) to Pd(0) is irre-
versible.55 For irreversible electrode reactions, the product of the charge transfer co-
efficient of the electrode reaction and the number of reaction electrons in the control
step satisfies the following equation:56
 
Ep  E  = 1:857 RT=ana F; (Equation 7)
p=2

where Ep is the peak potential (V); Ep/2 is the half-peak potential at half the peak current
value (V); R is the gas constants (8.314 J mol1$K1); n is the number of electrons gained
and lost by electrode reaction (n = 2 in this electrode reaction); F is the Faraday
constants (96,500 C mol1); a is the charge transfer coefficient of the electrode
reaction; and na is the number of reaction electrons in the control step. For the irrevers-
ible electrode reaction, when the electrochemical reaction is controlled by the
diffusion step, the reduction peak current and the scanning rate satisfy the following
relationship:
1=2
Ip = 0:4958nFC0 AD1=2 ðana FvÞ=RTÞ ; (Equation 8)

where Ip is the reduction peak current (A); C0 is the initial concentration of reactants in
solution (50 mol cm3); A is the true surface area of working electrode (0.75 cm2); D is
the diffusion coefficient of reactants in solution (cm2$s1); and v is the scanning rate (V$s).

Simulated recovery process

In the simulated recovery process of Pd and Au, the same mass of metal wires and
salt aqua regia were mixed for leaching in the same way as that in the cyclic
voltammetry curve section. The concentration of dissolved metals was measured
by ICP-MS to calculate the dissolution ratios of Pd and Au. Constant potential and
constant current electrodeposition using a three-electrode system were used for
Pd and Au simulants, respectively. The electrodeposition recovery was calculated
as follows:

R% = ðC1  C2 Þ=C1 3 100%; (Equation 9)

where C1 is the concentration of metals after dissolution and before electrodeposi-
tion, and C2 is the concentration of metals after electrodeposition.

The current efficiency was calculated as follows:

 Z  Z 
hPd = m0 c It 3 100% = nF=M 3 m0 It 3 100%; (Equation 10)

hAU = m0 =cIt 3 100% = nF=M 3 m0 =It 3 100%; and (Equation 11)

c = nF=M; (Equation 12)

where ƞPd and ƞAu are the current efficiency of Pd and Au, respectively; m is the mass
of electrodeposited product at working electrode (g); c is the electrochemical equiv-
alent (g$A1$h1), that is, the amount of electrolytic substance per unit of power; I is
the current (A); t is the electrodeposition time (h); n is the number of electrons gained
and lost by electrode reaction (n = 2 for Pd, and 3 for Au); F is the Faraday constant

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(96,500 C mol1 = 96,500 A$s$mol1 = 26.8 A$h$mol1); and M is the molar mass of
the reactant (g$mol1, 106.42 for Pd, and 196.97 for Au).

Besides, cyclic stability experiments of aqua regia were investigated. The salt aqua re-
gia used to dissolve the metal wire was defined as cycle 0, and the solution after elec-
trodeposition of the metals was defined as cycle 1. The cycle 1 salt aqua regia was then
repeated as the cycle 0 to perform the cycle test. A total of three cycles were performed.

Recovering Pd and Au from spent catalysts

At first, the spent Pd and Au catalysts were performed by microwave digestion to
determine the metal contents by ICP-MS. 1 g Pd and Au catalysts were dissolved
in salt aqua regia whose Al(NO3)3$9H2O to NaCl molar ratios were 1:0.5 and 1:1
at 80
C and 500 RPM for 30 min with a solid-to-liquid ratio of 1:10. After centrifuga-
tion separation of undissolved catalysts, the dissolution ratios of Pd, Au, and other
metals were determined by ICP-MS. Finally, the filtrates of both Pd and Au catalysts
were subjected to constant current electrodeposition using the three-electrode sys-
tem to obtain precious metal products. The products obtained on the electrode
were microwave digested and then tested by ICP-MS to calculate the electrodepo-
sition recovery of precious metals.

SUPPLEMENTAL INFORMATION
Supplemental information can be found online at https://doi.org/10.1016/j.xcrp.
2022.101159.

ACKNOWLEDGMENTS
This work is supported by the National Natural Science Foundation of China (no.
U2067213), the Natural Science Foundation of Zhejiang Province (LR21B060001),
and the Science and Technology Program of Institute of Zhejiang University-Quzhou
(no. IZQ2021KJ2014 and IZQ2021KJ2004).

AUTHOR CONTRIBUTIONS
Conceptualization, C.X.; experimental investigation, A.D., M.L., and C.L.; calcula-
tions, X.Z. and L.L.; writing – original draft, review & editing, C.X., A.D., M.L., and
C.L.; supervision, C.X. and A.D.

DECLARATION OF INTERESTS
The authors declare no competing financial interest.

Received: August 29, 2022

Revised: September 29, 2022
Accepted: November 2, 2022
Published: November 30, 2022

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