nature chemistry

Article https://doi.org/10.1038/s41557-024-01506-z

Upcycling of polyethylene to gasoline

through a self-supplied hydrogen strategy in
a layered self-pillared zeolite

Received: 19 July 2023 Ziyu Cen 1,2, Xue Han 3 , Longfei Lin 1,2 , Sihai Yang 4,5 ,
Wanying Han6, Weilong Wen1,2, Wenli Yuan1, Minghua Dong1,2, Zhiye Ma1,2,
Accepted: 11 March 2024
Fang Li6, Yubin Ke7, Juncai Dong 8, Jin Zhang8, Shuhu Liu8, Jialiang Li8, Qian Li9,
Published online: xx xx xxxx Ningning Wu9, Junfeng Xiang 9, Hao Wu10, Lile Cai10, Yanbo Hou10,
Yongqiang Cheng 11, Luke L. Daemen11, Anibal J. Ramirez-Cuesta 11,
Check for updates
Pilar Ferrer 12, David C. Grinter 12, Georg Held 12, Yueming Liu6 &
Buxing Han 1,2,6,13

Conversion of plastic wastes to valuable carbon resources without using

noble metal catalysts or external hydrogen remains a challenging task.
Here we report a layered self-pillared zeolite that enables the conversion of
polyethylene to gasoline with a remarkable selectivity of 99% and yields of
>80% in 4 h at 240 °C. The liquid product is primarily composed of branched
alkanes (selectivity of 72%), affording a high research octane number of
88.0 that is comparable to commercial gasoline (86.6). In situ inelastic
neutron scattering, small-angle neutron scattering, solid-state nuclear
magnetic resonance, X-ray absorption spectroscopy and isotope-labelling
experiments reveal that the activation of polyethylene is promoted by
the open framework tri-coordinated Al sites of the zeolite, followed by
β-scission and isomerization on Brönsted acids sites, accompanied by
hydride transfer over open framework tri-coordinated Al sites through a
self-supplied hydrogen pathway to yield selectivity to branched alkanes.
This study shows the potential of layered zeolite materials in enabling the
upcycling of plastic wastes.

The plastic wastes are projected to exceed 25 billion tonnes by 20501–5, reactor and/or down-stream processing14. Emerging approaches to
requiring urgent developments of approaches to chemically recycling transform polyolefins into the fuel-range hydrocarbons offer great
plastic wastes6–10. The key to convert polyolefins is to break their inert industrial potentials. However, fuel-range alkanes have a higher H/C
C(sp3)–C(sp3) bonds and to place effective control of selectivity to desir- ratio than polyolefins (~2.2–2.3 and 2.0, respectively). Therefore, an
able products. A state-of-the-art toolbox for generating single products external H2 source or hydrogen enriched co-reactants is required to
from polyolefins includes partial dehydrogenation and tandem isomer- promote the conversion. For example, with high-pressure H2, liquid
izing ethenolysis to yield propylene11, an electrified spatio-temporal fuels can be generated from polyolefins through hydrogenolysis or
heating approach to generate monomers in far-from-equilibrium state12 hydrocracking on noble metal catalysts15–21 (Fig. 1a and Supplementary
and pairing chemical oxidation and biological funnelling to form poly- Table 1). Likewise, the addition of hexane (H/C ratio 2.33)22 or isopentane
hydroxyalkanoates13. However, these strategies critically rely on the (H/C ratio 2.40)23 in depolymerization of polyolefins makes fuels by
use of organometallic complexes, noble metal catalysts, a complex alkane metathesis or tandem cracking and alkylation. The absence of

A full list of affiliations appears at the end of the paper. e-mail: xue.han@bnu.edu.cn; linlongfei@iccas.ac.cn; sihai.yang@pku.edu.cn; hanbx@iccas.ac.cn

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a
Noble metals m Noble metals Noble metals
n
n –m C1–C40
n-alkanes
b

Grind and mix

with LSP zeolite 240 °C, 4 h

Gasoline in CH2Cl2
Waste PE Yield 81%, selectivity 99%

Unsaturated polymers Iso-alkenes

SSH SSH

SSH SSH

Iso-alkanes

PE LSP zeolite

n β-scis/Isom x x
C4–C12 alkenes C4–C12

m m

R R

Fig. 1 | Representative routes of chemical conversion of polyolefins. under mild conditions via an SSH strategy and the resultant gasoline shows
a, Conversion of PE to n-alkanes through hydrogenolysis over noble metal an unprecedented selectivity of 99% for direct use as a fuel. Habs, hydride
catalysts under high-pressure H2. b, Conversion of PE to gasoline on LSP zeolites abstraction; β-scis, β-scission; Isom, isomerization; Htf, hydride transfer.

external H2 or co-reactants in the reaction system is highly attractive β-scission and isomerization, resulting in commercial-grade gasoline
to industrial applications. Without the participation of external hydro- (alkenes <2 wt%) with a high research octane number of 88.0 (Fig. 1b).
gen source, only long-chain aromatics24 are formed over noble metal The inexpensive LSP-Z100 zeolites show excellent catalytic stability,
catalysts, and strategies using zeolites suffer from low polyethylene consolidating its great industrial potential.
(PE) conversion25 and generate mixtures of volatile hydrocarbons26–28.
Thus, powerful drivers exist to develop efficient, robust and economic Results and discussion
processes for the conversion of polyolefins to transportation fuels. Synthesis and characterization
In this Article, we report a self-supplied hydrogen (SSH) strat- A facile one-step hydrothermal reaction was conducted to syn-
egy to convert PE directly into gasoline with a selectivity of 99% and thesise LSP-Z100 using tetra(n-butyl)ammonium hydroxide as
yield of 81% over a unique layered self-pillared zeolite (LSP-Z100) at structure-directing agent (Methods, LSP-ZX refers to LSP zeolite
240 °C without using noble metals or any external hydrogen source with Si/Al ratio of X). It adopts MFI/MEL intergrowth structure with
(Fig. 1b). The layered structure endows LSP zeolites with extensive open self-pillared layers, which feature a large external surface area and a
framework tri-coordinated Al sites (oFTAl) as strong Lewis acid sites, series of mesopores (Fig. 2a–c, Supplementary Figs. 1 and 2 and Sup-
resulting in superior activity to activate the inert C–H bonds of PE to plementary Table 2). A similar structure was found with LSP-Z75 but
supply hydrogen internally. Time-resolved analysis, solid-state nuclear with reduced surface area and mesoporous volume (Supplementary
magnetic resonance (NMR), an isotope-labelling technique, X-ray Figs. 1 and 2 and Supplementary Table 2). A further decrease in the Si/
absorption spectroscopy and in situ inelastic neutron spectroscopy Al ratio prevents the formation of LSP structures. Previous literature
(INS) have revealed the SSH mechanism, where hydrogen is transferred shows that strong acid sites and shape selectivity of zeolites are impor-
from PE (or oligomers) to iso-alkenes formed by hydride abstraction, tant features for conversion of PE29, but conventional zeolites such as

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a
LSP-Z100 LSP-Z100 LSP-Z100

50 nm 20 nm 5 nm

HZSM-5 HZSM-5 HZSM-5

200 nm 20 nm 5 nm

b c 800 d
LSP-Z100 LSP-Z100 Experimental LSP-Z100
Adsorbed volume (STP) (mL/g)
HZSM-5 HZSM-5 Experimental HZSM-5
Cumulative fitted peak
600 Fited peak –102
Intensity (a.u.)

Intensity (a.u.)
400 –111 –92

–112 –104
200
–119
–93
0
5 10 15 20 25 30 35 0 0.2 0.4 0.6 0.8 1.0 −140 −130 −120 −110 −100 −90 −80

2θ (°) Relative pressure (P/P0) 29

Si chemical shift (ppm)

e f g
LSP-Z100 LSP-Z100 LSP-Z100
HZSM-5 HZSM-5 1,455 DTBPy@LSP-Z100
HZSM-5
1,545 DTBPy@HZSM-5 1,530

Intensity (a.u.)
Intensity (a.u.)

Intensity (a.u.)

150 °C 1,616
200 °C
3,610
250 °C 3,370

350 °C

450 °C 3,740

120 100 80 60 40 20 0 −20 −40 −60 −80 1,580 1,540 1,500 1,460 1,420 3,600 3,200 2,800 2,400 2,000 1,600
27
Al chemical shift (ppm) Wavenumber (cm–1) Wavenumber (cm–1)
27
Fig. 2 | Characterization of the catalysts. a, High-resolution transmission shapes. e, Solid-state Al NMR spectra of LSP-Z100 and HZSM-5. f, IR spectra
electron microscopy images of LSP-Z100 and HZSM-5, showing layered self- before and after adsorption of pyridine at variable temperatures on LSP-Z100
pillared structure of LSP-Z100. Intermittent lattice fringes (white arrowheads) and HZSM-5. The dashed lines indicate vibrational peaks of pyridine molecules
suggest that mesopores exist throughout LSP-Z100. Note that three sets of adsorbed on Brönsted acid sites (1545 cm–1) and Lewis acid sites (1455 cm–1).
transmission electron microscopy images were taken at different magnifications. g, IR spectra before and after adsorption of DTBPy at 150 °C on LSP-Z100 and
b, X-ray diffraction patterns of LSP-Z100 and HZSM-5. c, N2 adsorption/ HZSM-5. The dashed lines indicate vibrational peaks of zeolite silanol group
desorption isotherms of LSP-Z100 and HZSM-5. d, 1H–29Si cross-polarization/ (3740 cm–1), Brönsted acid site (3160 cm–1) and adsorbed DTBPy molecule
Magic Angle Spinning Nuclear Magnetic Resonance (MAS NMR) spectra of (3370, 1616 and 1530 cm−1). a.u., arbitrary units.
LSP-Z100 and HZSM-5, and de-convolution of 29Si-NMR spectra by Gaussian line

HZSM-5 and HY alone showed little activity due to the narrow pores a similar amount of acid sites to HZSM-5 (Supplementary Fig. 3 and
and limited acid sites on the external surface. Mesoporous materi- Supplementary Tables 4 and 5), but shows higher amounts of strong
als, such as MCM-41 and SAB-15, have only weak acid sites, which are Lewis acid sites (Fig. 2f, Supplementary Fig. 4 and Supplementary
incapable of cleaving the C(sp3)–C(sp3) bonds under mild conditions. Table 5). Moreover, the acid sites of LSP-Z100 are significantly more
Two-dimensional structured materials are emerging catalysts showing accessible to bulky molecules as confirmed by 2,6-di-tert-butylpyridine
unique advantages, such as high external surface area, but have not (DTBPy) infra-red (IR) spectroscopy (Fig. 2g, Supplementary Fig. 5
been used for PE upcycling. Conventional two-dimensional materials and Supplementary Discussion 1). This is in contrast to the conven-
can hardly afford shape selectivity due to unrestricted surface. LSP tional porous materials (for example, HZSM-5, HY, MCM-41 and
zeolites have uniquely pillared structures and accessible acid sites for SBA-15), which have either limited accessibilities of acid sites or no
bulky molecules, distinctly different from conventional zeolites. Com- strong acid sites.
pared with the commercial HZSM-5, LSP-Z100 showed much higher N2
adsorption (Fig. 2c) and higher content of Q3 [Si(OSi)3(OH)] (−102 ppm) Catalytic performance
and Q2 [Si(OSi)2(OH)2] (−92 ppm) Si species (Fig. 2d and Supplementary For a typical reaction, high-density PE (HDPE) was mixed with the
Table 3), due to its distinct LSP network and the presence of mesopores catalyst in a mass ratio of 5:1 and the mixture was loaded into an auto-
(Fig. 2a). LSP-Z100 exhibits trace extra-framework Al sites (Fig. 2e) and clave. After purging with N2, the autoclave was heated to 240 °C for 4 h.

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Table 1 | Summary of the HDPE conversion and product yields over various catalystsa

Entry Catalysts Conversion (%) Yield (%) Components of gasoline range products (%)
C1–C3 C4–C12 >C 12
b
n-Alkanes i-Alkanes Alkene Cycloalkanes Aromatics
(gasoline range)

1 HZSM-5 35.1 0.6 34.5 0.0 16.0 43.0 27.8 5.7 7.5
2 HY 3.6 0.1 3.5 0.0 3.3 78.3 3.9 4.1 10.4
3 USY 8.6 0.1 8.5 0.0 3.8 77.2 1.0 6.1 11.9
4 Meso-HY 19.7 0.4 19.3 0.0 5.2 79.5 4.7 5.3 5.3
5 MCM-41 9.0 0.3 8.7 0.0 8.1 78.5 5.2 3.1 5.1
6 SBA-15 <1 – – – – – – – –
7 LSP-Z75 78.3 1.8 76.5 0.0 10.1 71.7 3.2 4.5 10.5
8 LSP-Z100 81.8 0.6 81.2 0.0 11.7 72.5 1.4 4.3 10.1
9 LSP-Z100 c
90.2 3.0 87.2 0.0 14.6 68.7 0.8 4.2 11.7
10 Commercial gasolined – – – – 9.8 44.1 7.4 6.2 20.3
11 Fresh FCC catalyst 5.8 0.2 5.6 0.0 8.5 86.7 4.4 0.4 0.0
12 Spent FCC catalyst <1 – – – – – – – –
13 Short b-axis ZSM-5 12.0 0.2 11.8 0.0 10.1 21.4 53.4 6.7 8.5
14 [C4Py]Cl–AlCl3 <1 – – – – – – – –
15 Ru/C <1 – – – – – – – –
16 Pt/γ–Al2O3 <1 – – – – – – – –
17 Pt/WO3/ZrO2 + HY(30) 12.5 0.3 12.2 0.0 7.9 81.2 1.2 0.4 9.3
a
Reaction conditions, catalyst, 0.09 g; HDPE, 0.45 g; temperature, 240 °C; reaction time, 4 h; N2 atmosphere, 0.1 MPa. bC12+ compounds in liquid products were not detected by GC. cReaction
time is 24.5 h. dCommercial gasoline with 12.2% ethanol as an additive.

The reaction was then ceased by cooling to room temperature, and SSH pathway
the products collected for analysis. Among all the tested microporous The time course of HDPE depolymerization over LSP-Z100 at 240 °C
(HZSM-5, HY and USY) and mesoporous (LSP, meso-HY, MCM-41 and was studied by analysing the products using gas chromatography (GC),
SBA-15) catalysts, only LSP zeolites exhibited substantial catalytic activi- GC mass spectroscopy (MS) and by analysing the solid residues using
ties (Table 1, entries 7–9, and Supplementary Table 6). Importantly, elemental analysis, 13C MAS NMR, 1H NMR and glow discharge electro-
LSP-Z100 gave a high conversion of HDPE of 81.8% (Table 1, entry 8) spray ionization (GD ESI) mass spectrometry. At 0.2 h (Fig. 3a), alkanes
and an unprecedented selectivity of >99% to C4–C12 compounds (gaso- and alkenes were observed, indicating that LSP-Z100 is extremely active
line range) with negligible C1–C3 compounds (<1%) (Supplementary to crack PE. Between 0.2–4 h, the yield of alkenes experienced a slight
Tables 7 and 8). This is attributed to the advantage that the formation increase and then decreased to <2%, whereas rapid formation of alkanes
of C4+ compounds, particularly branched C4+ compounds through continued until the completion of reaction when the yield of alkanes
A-type (tertiary–tertiary) or B-type (secondary–tertiary) β-scission, reached 75%. From 4 h to 24.5 h, secondary cracking of the C6–C9 prod-
is energetically more favourable30,31 and can rapidly take place at mild ucts took place (Extended Data Fig. 2), as well as cyclization and aroma-
reaction temperatures (Supplementary Discussion 2). With a prolonged tization to produce only a small fraction of aromatics and cycloalkanes
reaction time of 24.5 h, the yield of gasoline increased to 87.2% (Table 1, (Fig. 3a). The 13C NMR spectrum of the solid residue from the reaction
entry 9). Compared with commercial gasoline, the liquid product showed a clear signal of methyl group (18 ppm), branched (21 ppm)
from this reaction is of premium quality in terms of higher content of and unsaturated species (120–150 ppm) (Fig. 3b, Supplementary Fig. 6,
branched alkanes (44.1% versus 72.5%), comparable research octane Supplementary Tables 11 and 12 and Supplementary Discussion 3). This
number (86.6 versus 88.0, Supplementary Table 9) and notably lower indicates that part of PE undergoes partial cracking, isomerization and
contents of contaminating aromatics (20.3% versus 10.1%) and olefins hydride transfer to form unsaturated oligomers (H/C <2) as internal
(7.4% versus 1.4%) (Table 1, entries 8 and 10, and Extended Data Fig. 1). hydrogen source. The SSH pathway is validated by elemental analysis
The reduced olefin content is probably related to the shortened diffu- of products and reaction residues. As shown in Fig. 3c, C and H content
sion path in LSP-Z100. This suggests that intermediate alkenes diffuse transfer from the solid residue to the product with the increase of reac-
more rapidly within the catalyst, facilitating adequate interaction with tion time. The H/C ratio of products raises from initially 2.03 to ~2.2 as
active sites in a confined system. Consequently, this promotes the the reaction starts, while the H/C ratio of residue decreases during the
transformation of intermediate alkenes into alkanes (that is, the main reaction, confirming the internal hydrogen transfer (Fig. 3d). The H/C
component of gasoline). For instance, reducing the particle size of ratio of total hydrocarbons (products and solid residues) maintained
HZSM-5 from 4 μm to 200 nm resulted in a decrease in selectivity for at ~2.03 throughout the reaction (Fig. 3c and Supplementary Table 13)
alkenes (Supplementary Table 10, entries 1 and 2). A series of reported and total mass balances for all hydrocarbons typically closed to within
best-behaving catalysts (for example, fresh fluid catalytic cracking 1.8% (Supplementary Table 14). The SSH strategy inevitably generates
(FCC) catalysts27, spent FCC catalysts27, short b-axis ZSM-5 (ref. 28), a small amount (18.2%) of solid residues (H/C <2). The solid residues
[C4Py]Cl–AlCl3(ref. 23), Ru/C (ref. 16), Pt/γ–Al2O3 (ref. 24) and Pt/WO3/ were treated with hydrofluoric acid (HF) to remove the zeolite, and the
ZrO2 + HY(30) (ref. 21)) have also been tested in our system (Table 1, remaining hydrocarbons were separated through dichloromethane
entries 11–17), but they show regrettable activity due to the lack of (DCM) extraction (Supplementary Table 15) for further characteriza-
external hydrogen source or additives. tion by 1H NMR, 13C NMR and GD ESI mass spectrometry. The fraction

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a 100 100 b c
60 C Products
2.6
Residue
H

Content of C or H (mmol)
80 80 In total
40 2.4
Simulated
Conversion (%)

Intensity (a.u.)
20
60 60 24.5 h 2.2

H/C ratio
Yield (%)
Products
Isoalkane 0
7.5 h Residue 2.0
40 Alkene 40
n-Alkane 20
4h 1.8
Aromatics
20 Cycloalkane 20 1h 40
1.6
HDPE 60
0 0 1.4
0 5 10 15 20 25 160 140 120 100 80 60 40 20 0 0 0.1 2.5 4 7.5 24.5
Time (h) δ (ppm) Time (h)

d PE e f
Habs Habs 10,000.00 3.2
β-scis β-scis LSP-Z100 + HDPE
1,000.00 0.5 h Dm(LSP-Z100) = 2.69
2h
Unsaturated 2.8

Fractal dimensions
Htf
Olefins n-Alkanes 100.00 4h
Intensity (cm–1)

oligomers
LSP-Z100 2.68
Isom Isom 10.00 2.4 2.55

i-Unsaturated Htf 2.31

oligomers i-Olefins i-Alkanes 1.00

2.0
0.10
Dm(LSP-Z100 + HDPE) = 2.03
SSH [H] 0.01
1.6
0.01 0.10 1.00 0 1 2 3 4 5
Q (Å–1) Reaction time (h)

g h i
Virgin PE Product Residue Products 100
100 C
60 Residue
81.8 77.9 72.5 70.5 2.4
Content of C or H (mmol)

H In total 80

Yield of gasoline (%)

80 40
Percentage

2.2 H/C ratio 60

20 Products
60
100 81.8 77.9 72.5 Residue
0 40
40 2.0
20

20 40 20
1.8
18.2 18.2 22.1 22.1 27.5 27.5 29.5 60
0 0
R1,0 R1,t R2,0 R2,t R3,0 R3,t R4,0 R4,t PE 1 2 3 4 5 1 2 3 4 5
Cycles Cycles

Fig. 3 | Time course of conversion of HDPE over LSP-Z100 and stability of fractal dimensions of LSP-Z100, mixture of LSP-Z100 and HDPE, and reaction
LSP zeolites. a, The trends of conversion of PE and yield of products. Reaction of mixture at different reaction time obtained from SANS spectra. Simplified
conditions: catalyst, 0.09 g; HDPE powder, 0.45 g; reaction temperature, models of LSP-Z100 and HDPE are shown based on SANS results (LSP-Z100,
240 °C; N2, 0.1 MPa. b, Solid-state 13C NMR spectra of the reaction residue, orange; HDPE, grey; argon, cyan). g, A comparison of reactions 1–4 over LSP
showing the presence of unsaturated species and methylene group in residue zeolites at 240 °C for 4 h. After each reaction, the catalyst was used directly after
(32 ppm, Supplementary Fig. 6 and Supplementary Table 12). a.u., arbitrary drying. Fresh PE was added to maintain the same mass of hydrocarbons in Rx,0 for
units. c, Variation of C and H contents and H/C ratio of short chain products each reaction. Rx,0, before reaction; Rx,t, after reaction, where x = 1,2,3,4. Atomic
and solid residues as a function of reaction time. Bars with dots are attributed utilization = (sum of products/total added virgin PE) × 100%. h, The variation of
to unreacted PE. d, Scheme of PE depolymerization pathway and SSH pathway. C and H content and H/C ratio of products and solid residue in reactions 1–4 over
Habs, hydride abstraction; β-scis, β-scission; Isom, isomerization; Htf, hydride LSP zeolites at 240 °C for 4 h. i, Comparison of gasoline yield over five cycles
transfer. e, SANS spectra for HDPE and reacted HDPE at 190 °C. All SANS spectra of reactions over LSP zeolite at 240 °C for 4 h. After each cycle, the catalyst is
shown are after the subtraction of SANS spectrum of the empty cell. f, Mass calcined at 550 °C under air.

insoluble in DCM comprises unreacted PE (Supplementary Fig. 7). The the reaction (Fig. 3e). The decrease on intensity of neutron scattering in
DCM-soluble portion is predominantly composed of long-chain alkylar- the high Q region (>0.2 Å−1) is due to lower incoherent scattering caused
omatics and long-chain alkylcyclic compounds (unsaturated oligomers), by hydrogen atom, suggesting the cracking of HDPE and evaporation
with a molecular weight range between 100 and 1,000 (Supplementary of generated light hydrocarbons (Fig. 3e). In addition, the change of
Figs. 8–11 and Supplementary Tables 16 and 17). The observation of these mass fractal dimension in the Q region of 0.02–0.2 Å−1 reflects that the
unsaturated oligomers further corroborates the proposed SSH mode. components of reaction mixture had altered during reaction (Fig. 3f
Thermogravimetric analysis (TGA) shows that the yield of coke is only and Supplementary Fig. 14). Before 4 h, the mass fractal dimension
0.58% (Supplementary Figs. 12 and 13 and Supplementary Discussion 4) increased gradually, indicating the surface-assisted cracking of PE
and thus the residual comprises primarily unsaturated oligomers and chains around active sites. In this period, the viscosity of the system
uncracked PE, probably restricted by hindered diffusion. decreases because the cracking of long-chain PE into shorter chain
In situ small-angle neutron scattering (SANS) was applied to oligomers32. At 4 h, the mass fractal reached 2.68 (close to 2.69, the
investigate the diffusion of PE and intermediates to the catalysts during mass fractal dimension of LSP-Z100), indicating the approximate

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depletion of coil chain of PE upon reaction. This reveals the hindered 64 and 68 ppm) exhibit slight shifts compared with that of HZSM-5
diffusion of residual oligomers to the active sites, consistent with the (63, 65 and 69 ppm), since the Al sites on layered structure of LSP-Z100
catalysis and TGA results. are extensively open and have different chemical environment, con-
To promote the diffusion and atomic economy, fresh PE (81.8%) sistent with the DTBPy IR spectroscopy analysis (Fig. 2g). Thus, the
is mixed with the reaction residue (18.2%) after 4 h (R1) and undergoes super-strong Lewis acid sites (strongly bound with pyridine even at
a new cycle of reaction (R2) (Fig. 3g). The newly added PE acts as sol- 450 °C as shown in Fig. 2f) of LSP-Z100 originate from oFTAl. Moreover,
vent to facilitate mass transport of residual oligomers as well as reac- the hydride transfer between 2-methylbutane (i-C5H12) and deuterated
tion substrate in the new reaction. Importantly, the result of the new hexane (C6D14) has been studied at 240 °C to demonstrate the activity
cycle is comparable with the first reaction (Fig. 3g and Supplementary of oFTAl. On LSP-Z100, i-C5H12-xDx (x = 1–10), C6D14–yHy (y = 1–3) were
Table 18), suggesting that the previous reaction residues can be con- observed (Fig. 4e–h, Extended Data Figs. 3 and 4, Supplementary
verted to products with fresh PE, although another solid residue (22.1%) Figs. 20 and 21, Supplementary Tables 22 and 23 and Supplementary
was formed from the new cycle. This reveals the key role of promoted Discussion 5), while HZSM-5 shows little activity, indicating that the
diffusion of residues, thus preserving the activity of LSP-Z100. After hydride abstraction and hydride transfer occur primarily on oFTAl. By
four cycles of reaction, the yield of gasoline is maintained at >70% extending the reaction time for HZSM-5 to 8 h, a similar deuteration
and the total atomic utilization is as high as 91% (Fig. 3g). The H/C level of 2-methylbutane and selectivities of products were observed,
contents are balanced during the four reactions (Fig. 3h and Supple- compared with that of LZP-Z100 achieved in 2 h (Supplementary
mentary Table 19) and little coke was formed (~0.5%, Supplementary Figs. 22–25), thus confirming the higher efficiency of LSP-Z100 in
Table 20 and Supplementary Fig. 15) owing to the widely opened pores hydride abstraction and transfer. Controlled experiments on LSP-Z100
of LSP zeolites to prevent coke formation. The excellent stability of with decreased accessible acid sites (poisoned by DTBPy) or oFTAl sites
LSP-Z100 was further demonstrated by cycling testing (the residues (partially removed by ammonium hexafluorosilicate) demonstrated a
were removed by calcination before next cycle), in which the yield of notable drop in PE conversion (Supplementary Fig. 26, Supplementary
gasoline remained at 80% over five cycles (Fig. 3i). The characteriza- Tables 10 and 24 and Supplementary Discussion 6). Also, the contribu-
tion of used catalysts confirms little change to the structure and acidic tion of silanol groups with weak Lewis acidity to the conversion of PE is
sites, demonstrating the excellent structural stability of LSP-Z100 limited (Supplementary Fig. 27 and Supplementary Table 10, entries
(Supplementary Figs. 16–18). Thus, LSP-Z100 enables the success of 5–9). These results demonstrate that oFTAl and accessible Brönsted
SSH mode for conversion of PE to gasoline with coke resistance and acid sites play the primary role in the PE conversion.
high atomic utilization.
Study of reaction mechanism
Identification of active sites To further understand the reaction mechanism at an atomic level,
The local environment of the acid sites Si–O–Al was interrogated in situ INS (Supplementary Fig. 28 and Supplementary Discussion
through near-edge X-ray absorption fine structure (NEXAFS) analysis 7), combined with density functional theory (DFT) calculations, was
at the oxygen K edge. The absorption edges of LSP-Z100 were consist- employed to investigate the conversion of HDPE on LSP-Z100. The
ent with those of SiO2 and Al2O3 (Fig. 4a). The peak at 534 eV is due to INS spectrum of activated LSP-Z100 gave a clean background with
adsorbed water in the materials33. The region between 538 eV and 543 eV no prominent features at 0–1,600 cm−1 (Supplementary Figs. 29 and
(white line) in the O K-edge NEXAFS spectrum is attributed to transi- 30). The mixture of HDPE with LSP-Z100 showed a similar spectrum to
tions from O 1s to O 2p anti-bonding states hybridized with Si 3s, Si 3p, that of the bare HDPE, indicating little interaction between HDPE and
Al 3s or Al 3p character34–36. To understand the interaction between acid LSP-Z100 upon mixing at room temperature (Supplementary Fig. 30).
sites and guest molecules, the conversion of HDPE over LSP-Z100 was HDPE on LSP-Z100 underwent the first catalytic conversion at 190 °C
studied at different reaction stages. At stage 1 of reaction (190 °C for for 2 h (stage 1 of reaction, Fig.5a and Supplementary Fig. 31). In com-
2 h), LSP-Z100 showed decrease in the white line intensity (538–543 eV) parison with the spectrum of HDPE, the spectrum of stage 1 of the reac-
relative to bare LSP-Z100 (Fig. 4b and Supplementary Fig. 19), suggest- tion showed a decrease in intensity at 130, 201 and 726 cm−1, which are
ing a partial filling of the O 2p anti-bonding orbital. This confirms that assigned to the in-plane and out-of-plane skeletal stretching of HDPE,
the generated unsaturated species (for example, alkenes) during the and to the methylene (–CH2–) rocking, respectively. This suggests the
reaction were bound to the Si–O–Al sites by donating electrons to the scission of C–C bonds and depolymerization of PE chains. Meanwhile,
O 2p anti-bonding orbital. In addition, the increase in intensity in the a broad feature at low energy (below 200 cm−1) appeared, suggesting
region of 545–555 eV is due to scattering from the adsorbed unsaturated that the intermediate species were disordered over the catalyst surface
species on Si–O–Al sites. With the reaction ongoing (stage 2 of reaction, showing restricted translational and rotational dynamics. In addi-
230 °C for 1 h, Fig. 4b), the white line intensity increased, indicating the tion, new peaks at 212, 235, 255, 266, 336, 440, 913 and 971 cm−1 were
adsorbed alkenes are saturated because of hydride transfer reaction. observed. The appearance of peaks at 212–266 cm−1 (assigned to methyl
Importantly, at the stage 3 of reaction (240 °C for 2 h), the intensity torsion, Supplementary Table 25) further confirms the cleavage of PE
was closed to bare LSP-Z100, indicating the complete regeneration of chains. Notably, the overall spectrum profile of stage 1 of reaction is
Si–O–Al sites upon conversion of alkenes to alkanes that could desorb consistent with that of adsorbed unsaturated oligomers (Fig. 5b and
readily from the catalysts. Supplementary Discussion 8), which is in excellent agreement with
The structures of active sites were further investigated by 31P NMR the formation of oligomers upon cracking of PE as confirmed by 13C
spectroscopy of trimethylphosphine oxide (TMPO) as a probe mol- NMR in the time course study. Specifically, shoulder peaks at 212, 255
ecule37. LSP-Z100 possesses a large amount of FTAl sites, which act as and 266 cm−1 were identified as methyl torsion of 2-methylpentane
Lewis acid sites to coordinate with lone pair electrons of basic probe and 3-methylpentane (Fig. 5c, Supplementary Fig. 32 and Supple-
molecule (64 ppm, TMPO ∙ ∙∙Al(OSi)3; 62 ppm, TMPO ∙ ∙∙Al(OSi)2(OH); mentary Table 25) and the peaks at 336 and 440 cm−1 as the skeletal
68 ppm, TMPO ∙ ∙∙Al(OSi)(OH)2) (Fig. 4c,d and Supplementary Table 21). stretching modes of short alkanes (Fig. 5b, Supplementary Fig. 32 and
In contrast, the spectrum of TMPO adsorbed on HZSM-5 shows higher Supplementary Table 25). This result indicates that PE was activated
intensity of TMPOH+ ions protonated by Brönsted acid sites (76 ppm) via hydride abstraction on oFTAl and underwent β-scission/isomeri-
and less prominent signal of Lewis acid coordinated molecules (63– zation/hydride transfer to generate iso-alkanes. Although oFTAl are
69 ppm). This result is consistent with the Py-IR experiment that shows able to activate C(sp3)–H of PE/alkanes, the alkanes produced can
higher L/B ratio of LSP-Z100 than HZSM-5 (Fig. 2f and Supplementary readily desorb as supported by the INS spectra of adsorbed alkanes
Table 5). In addition, the peaks related to FTAl sites of LSP-Z100 (62, on the LSP-Z100 (Extended Data Fig. 5a,b). In contrast, alkenes bound

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a 4 b 1.8 c
LSP-Z100 Stage 3 Experimental LSP-Z100
1.6 Experimental HZSM-5
SiO2 Stage 2

Normalized absorption (a.u.)

Normalized absorption (a.u.)

Stage 1 Cumulative fitted peak

3 Al2O3 1.4
Bare LSP-Z100 Fitted peak 64

Intensity (a.u.)
1.2
74 68 62
1.0
2
0.8 89
0.6
76 65
1
0.4 63
83 69
0.2

0 0
530 535 540 545 550 555 560 565 570 530 535 540 545 550 555 560 565 570 100 90 80 70 60 50 40
31
Energy (eV) Energy (eV) P chemical shift (ppm)

d e h
Htf reaction on LSP-Z100
Htf reaction on HZSM-5
II
I
Intensity (a.u.)

III IV V

1.8 2.0 2.2 2.4 2.6 2.8

Retention time (min)

f g
I@LSP-Z100: i-C5H12+i-C5H12-XDX II@LSP-Z100: C6D14+C6D14-yHy
I@HZSM-5: i-C5H12+i-C5H11D II@HZSM-5: C6D14+C6D13H
Normalized intensity (a.u.)
Normalized intensity (a.u.)

71 72 73 74 75 76 77 78 79 80 81 82 83 84 94 95 96 97 98 99 100 101 102

m/z m/z

Fig. 4 | Identification of active sites of LSP-Z100 by NEXAFS, NMR and of i-C5H12/C6D14 hydride transfer reactions by LSP-Z100 and HZSM-5. I–V are
isotope-labelling technique. a, O K-edge NEXAFS for LSP-Z100, SiO2 and Al2O3. mainly composed of i-C5H11D, C6D13H, i-C5D11H, i-C6D13H and C6D12H2, respectively
The absorption edges of LSP-Z100 were consistent with those of SiO2 and Al2O3. (Extended Data Figs. 3 and 4). f, Mass spectra of 2-methylbutane after reaction on
b, O K-edge NEXAFS spectra for LSP-Z100 before reaction and LSP-Z100 during HZSM-5 and LSP-Z100. g, Mass spectra of hexane after reaction on HZSM-5 and
the reaction. c, 31P MAS NMR spectra of LSP-Z100 and HZSM-5 loaded with LSP-Z100. h, Scheme of i-C5H12/C6D14 hydride transfer reactions. Habs, hydride
TMPO. d, View of structure of Al sites with adsorption of TMPO. e, GC traces abstraction; a.u., arbitrary units.

strongly to active sites to promote their further conversion with SSH A full catalytic circle can be established (Fig. 5f). Upon adsorp-
(Extended Data Fig. 5c). tion on the LSP zeolite, PE is activated via hydride abstraction38,39
Then, the stage 2 of reaction was studied (230 °C for 1 h, Fig. 5a). on oFTAl or via protonation on the Brönsted acid sites40 to give
The very strong peak at 235 cm−1, corresponding to the torsional mode carbenium ions or carbonium ions as the initiation step. The carbo-
of oligomers, decreased notably in intensity. Meanwhile, the peaks at nium ions formed on the Brönsted acid sites are unstable, rapidly
212 and 255 cm−1, corresponding to the methyl torsion of iso-alkanes, collapsing to afford carbenium ions along with H2 or alkanes. The
grew in intensity. This result suggests the rapid conversion of activated isotope-labelling reactions (Fig. 4e–h) suggest that the activation via
HDPE or oligomers to iso-alkanes on the zeolite via β-scission/isomeri- hydride abstraction on oFTAl dominates at 240 °C. Then the activated
zation/hydride transfer reactions. However, the peaks of HDPE (130, PE (that is, the carbenium ion originated from hydride abstraction
201 and 726 cm−1) were still observed. Finally, the stage 3 of reaction or carbonium ion collapse) binds strongly to the Brönsted acid sites
was also investigated (240 °C for 2 h, Fig. 5a). The peaks at 235 and and undergoes rapid β-scission and skeletal isomerization via a
726 cm−1 disappeared and the peaks at 212, 255 and 266 cm−1 increased three-membered ring structure41–43, followed by intramolecular
dramatically in intensity. The spectrum of stage 3 of reaction showed hydrogen transfer to generate stable tertiary carbenium ions. Mean-
notable similarity with iso-hexanes (Fig. 5d,e), confirming the efficient while, oFTAl abstract hydrogen from PE or oligomers. Subsequen-
transformation of HDPE into iso-alkanes. tially, tertiary carbenium ions react with the SSH through hydride

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a Neutron energy loss (meV) b Neutron energy loss (meV) c Neutron energy loss (meV)
0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180 200 0 10 20 30 40 50

Stage 3 Adsorbed 2-MP Adsorbed 2-MP

Stage 2 Adsorbed 3-MP Adsorbed 3-MP
Stage 1 Adsorbed unsaturated oligomer Adsorbed unsaturated oligomer
HDPE Stage 1 Stage 1
S (Q, ω) (a.u.)

S (Q, ω) (a.u.)
S (Q, ω) (a.u.)
255

212 266

235

0 200 400 600 800 1,000 1,200 1,400 1,600 0 200 400 600 800 1,000 1,200 1,400 1,600 0 50 100 150 200 250 300 350 400

Neutron energy loss (cm–1) Neutron energy loss (cm–1) Neutron energy loss (cm–1)

d Neutron energy loss (meV) e

0 20 40 60 80 100 120 140 160 180 200

Adsorbed 2-MP
Adsorbed 3-MP
Stage 3

PE, 201 cm–1 Oligomer, 235 cm–1

S (Q, ω) (a.u.)

255 PE, 130 cm–1 PE, 726 cm–1

Olig, 726 cm–1 3-MP, 212, 266 cm–1 3-MP, 384 cm–1 2-MP, 255 cm–1
0 200 400 600 800 1,000 1,200 1,400 1,600

Neutron energy loss (cm–1)

f n
n

n n

Fig. 5 | INS spectra for LSP-Z100 zeolite on the catalytic conversion of adsorbed 2-MP, adsorbed 3-MP and reacted HDPE (stage 3 of the reaction) over
HDPE and proposed reaction mechanism. a, A comparison of INS spectra for LSP-Z100. All INS spectra shown here are after the subtraction of INS spectrum
solid HDPE and reacted HDPE over LSP-Z100. b, A comparison of INS spectra of the empty cell and zeolite. e, Selected vibrational modes of PE, oligomers,
of unsaturated oligomers, adsorbed 2-methylpentane (2-MP), adsorbed 3-MP and 2-MP (C, grey; H, white) observed by experiments. f, The proposed
3-methylpentane (3-MP) and reacted HDPE (stage 1 of the reaction) over main reaction pathway for the conversion of PE to iso-alkane over LSP-Z100,
LSP-Z100. The INS spectrum of adsorbed unsaturated oligomer was generated by including initiation, cracking/isomerization and hydride transfer. Habs, hydride
1-butene adsorbed on LSP-Z100. The dosed 1-butene oligomerizes over LSP-Z100 abstraction; Prot, protonation; β-scis, β-scission; Isom, isomerization; Htf,
and unsaturated bonds of oligomer bind to Brönsted acid site to form carbenium hydrogen transfer.
ions. c, Enlarged spectra of b at 0–400 cm−1. d, A comparison of INS spectra of

transfer to yield iso-alkanes for facile desorption and the acid sites PE molecules through hydride abstraction on oFTAl sites, β-scission/
regenerated. isomerization on Brönsted acid sites and hydride transfer on oFTAl
sites, collectively resulting in the production of gasoline with both high
Conclusion selectivity and yield. Moreover, LSP zeolites show excellent catalytic
The LSP structures endow the materials with oFTAl sites and accessible performance for the production of commercial-grade gasoline from
Brönsted acid sites, which facilitate the SSH mode to activate bulk both low-density and high-density PE waste (Supplementary Fig. 33),

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Article https://doi.org/10.1038/s41557-024-01506-z

which account for about 25% of the plastic waste today. The potential 19. Chen, L. et al. Disordered, sub-nanometer Ru structures on CeO2
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39. Primo, A. & Garcia, H. Zeolites as catalysts in oil refining. Chem. Publisher’s note Springer Nature remains neutral with regard to
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Mesoporous Mater. 35–36, 11–20 (2000). Attribution 4.0 International License, which permits use, sharing,
41. Mooiweer, H. H., de Jong, K. P., Kraushaar-Czarnetzki, B., adaptation, distribution and reproduction in any medium or format,
Stork, W. H. J. & Krutzen, B. C. H. Skeletal isomerization of olefins as long as you give appropriate credit to the original author(s) and the
with the zeolite ferrierite as catalyst. Stud. Surf. Sci. Catal. 84, source, provide a link to the Creative Commons licence, and indicate
2327–2334 (1994). if changes were made. The images or other third party material in this
42. Trombetta, M. et al. FT-IR studies on light olefin skeletal article are included in the article’s Creative Commons licence, unless
isomerization catalysis: III. surface acidity and activity of indicated otherwise in a credit line to the material. If material is not
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361–373 (2019). © The Author(s) 2024

1
Beijing National Laboratory for Molecular Sciences, CAS Laboratory of Colloid and Interface and Thermodynamics, CAS Research/Education Center for
Excellence in Molecular Sciences, Center for Carbon Neutral Chemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
2
School of Chemical Sciences, University of Chinese Academy of Sciences, Beijing, China. 3College of Chemistry, Beijing Normal University, Beijing,
China. 4College of Chemistry and Molecular Engineering, Beijing National Laboratory for Molecular Sciences, Peking University, Beijing, China.
5
Department of Chemistry, University of Manchester, Manchester, UK. 6Shanghai Key Laboratory of Green Chemistry and Chemical Processes, State Key
Laboratory of Petroleum Molecular and Process Engineering, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai,
China. 7China Spallation Neutron Source, Institute of High Energy Physics, Dongguan, China. 8Institute of High Energy Physics, Chinese Academy of
Sciences, Beijing, China. 9Center for Physicochemical Analysis Measurements, Institute of Chemistry, Chinese Academy of Sciences, Beijing, China.
10
SINOPEC Research Institute of Petroleum Processing, Beijing, China. 11Neutron Scattering Division, Neutron Sciences Directorate, Oak Ridge National
Laboratory, Oak Ridge, TN, USA. 12Diamond Light Source, Harwell Science and Innovation Campus, Didcot, UK. 13Institute of Eco-Chongming,
Shanghai, China. e-mail: xue.han@bnu.edu.cn; linlongfei@iccas.ac.cn; sihai.yang@pku.edu.cn; hanbx@iccas.ac.cn

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Methods where [polyolefin]0 and [polyolefin]t denote the mass of polyolefin

Zeolite synthesis before and after reaction, respectively, and mi denotes the mass of
The LSP zeolites were synthesized using the published method44 product i. The 13C NMR spectra of solid resides show that they are
with modification. Aluminium isopropoxide was added into tetra- composed of unsaturated compounds and unreacted PE, and the lat-
ethyl orthosilicate. Tetra(n-butyl)ammonium hydroxide was added ter account for the majority (Fig. 3b and Supplementary Fig. 6). For
dropwise into the mixture. Then, sodium hydroxide aqueous solu- simplicity, all solid residues were treated as [polyolefin]t. This leads
tion and de-ionized water were added into the mixture. The compo- to slightly overestimated selectivity and underestimated conversion,
sition of the above mixture was 60 SiO2:0.30 Al2O3:18 TBAOH:0.75 but the yield is accurate.
NaOH:600 H2O:240 EtOH for LSP-Z100 and 60 SiO2:0.40 Al2O3:18 The stability test of LSP-Z100 was conducted for the conversion of
TBAOH:1.5 NaOH:600 H2O:240 EtOH for LSP-Z75. The sample name HDPE at 240 °C for 4 h. After each cycle of the reaction, LSP-Z100 was
of LSP-ZX refers to LSP zeolite synthesized from a clear sol with the collected, washed, dried and calcined at 550 °C in static air for 4 h. The
Si/Al ratio being X. After stirring for 12 h, the mixture for the synthesis regenerated catalyst was used for the next cycle of catalytic conversion.
of LSP-Z100 was sealed in an autoclave (50 ml) and heated for 88 h
in a pre-heated oven at 115 °C, and that for LSP-Z75 was sealed and NEXAFS
heated for 48 h at 120 °C. The product was centrifuged and washed by NEXAFS measurements were conducted at 4B7B station at Beijing
de-ionized water for several times until the pH is lower than 9. Then, Synchrotron Radiation Facility, and at beamline B07-B at Diamond
the product was dried at 70 °C for 12 h and calcined at 550 °C in static Light Source. The samples were collected after the reaction at differ-
air for 16 h. Ion exchange was conducted to exchange the Na+ sites by ent stages for NEXAFS measurements. In a typical sample preparation,
NH4+ using 1.0 mol l−1 ammonium chloride aqueous solution at 80 °C. 0.24 g of LSP zeolite and 0.04 g of HDPE were mixed and heated at
The process was repeated three times, and the solid was washed and 190 °C for 2 h under 0.1 MPa N2 for the stage 1 of reaction. The reaction
dried at 70 °C and calcined at 550 °C in static air for 4 h to produce the conditions were 230 °C for 1 h for stage 2 of the reaction and 240 °C for
protonated zeolite. 2 h for stage 3 of the reaction. The NEXAFS spectra of all samples were
For synthesis of HZSM-5, tetra(n-propyl)ammonium hydroxide collected under vacuum (or under 1 mbar He to avoid charging) at room
(TPAOH), aluminium isopropoxide and de-ionized water were mixed temperature using the total electron yield method.
and stirred at room temperature for 2 h. Tetraethyl orthosilicate was
added and then continued to stir for another 2 h, resulting in a gel with SANS
a chemical composition of 60 SiO2:0.43 Al2O3:15 TPAOH:900 H2O. The SANS was measured at China Spallation Neutron Source (CSNS). In a
gel was transferred and sealed in an autoclave (50 ml) and heated at typical experiment, LSP-Z100 powder was loaded into a quartz cuvette
170 °C for 48 h. The product was centrifuged and washed by de-ionized with 1 mm path length. The scattering intensity spectrum was collected
water for several times until the pH is lower than 9. Then, the product in Ar atmosphere at room temperature. Then, LSP-Z100 and HDPE were
was dried at 70 °C for 12 h and calcined at 550 °C in static air for 16 h. mixed with a mass ratio of 6:1 and the mixture was loaded into a quartz
The ion exchange procedure was conducted to exchange the Na+ sites cuvette in the Ar atmosphere. The temperature was raised from room
by NH4+ using 1.0 mol l−1 ammonium chloride aqueous solution at 80 °C. temperature to 190 °C. The spectra were collected at 0.5 h, 2 h and 4 h,
The process was repeated for three times, and the solid was washed and respectively at 190 °C. The background of Ar and quartz cuvette has
dried at 70 °C and calcined at 550 °C in static air for 4 h to produce H been subtracted, and the scattering intensity was normalized to an
form zeolite. The Si/Al ratio of HZSM-5 is 60 (Supplementary Table 4) absolute scale by a standard calibration procedure.
and particle size of HZSM-5 is 200 nm.
Inelastic neutron scattering
Catalytic conversion of polyolefins INS spectra were recorded on the VISION spectrometer at Spallation
The catalytic reaction was conducted in a 10 ml Teflon-lined stainless Neutron Source, Oak Ridge National Laboratory. VISION are indirect
steel autoclave. In a typical reaction, polyolefins (0.45 g) was mixed geometry crystal analyser instruments that provide a wide dynamic
with the catalyst (0.09 g) by grinding for 5 min before loading into the range with high resolution. In a typical experiment, the catalyst (~9 g)
autoclave. The autoclave was purged with N2 for three times and the was loaded into a flow-type stainless steel cell that can also be used
pressure regulated to ambient pressure. The reactor was then sealed as a static cell with all valves closed. The sample was heated at 450 °C
and heated to 240 °C in 30 min and held at this temperature for 4 h. (5 °C min−1 ramping) under He for 3 h to remove any remaining trace
Then, the reactor was cooled to room temperature. The gaseous prod- water before the experiment. Then, 1.5 g HDPE was mixed with acti-
uct was collected with a gas bag and analysed by a GC (Agilent 8890) vated catalyst in a glove box at room temperature. The reactions were
instrument equipped with a thermal conductivity detector (TCD), conducted at 190, 230 and 240 °C, respectively. After each reaction,
two flame ionization detectors, a HP-plot Al2O3 column, a HP PONA the cell was cooled for INS collection to detect the presence of pos-
column, a 5 Å molecular sieve column and two hayesep Q columns. sible reaction intermediates. All the INS spectra were collected after
Liquid products were dissolved in CH2Cl2 and analysed by GC Agilent the sample was cooled and stabilized at temperatures below 15 K.
8890 and GC–MS (Agilent 7890B-5977A MSD) equipped with a HP-5ms INS spectra of pure solid compounds for both starting material and
column. The standard curve method was used in quantification. Solid reaction products were collected at 5 K. The INS procedure is listed in
residue was heated at 80 °C for 12 h and analysed by TGA analyser. All Supplementary Fig. 28.
long-chain species that can not be evaporated below 220 °C are consid-
ered as unconverted PE. The conversion of polyolefin and selectivity DFT calculations
(S) and yield of products were calculated by the following equations: Simulation of the INS spectra of 1-butene, 2-methylpentane and
3-methylpentane has been conducted. Optimized geometry and vibra-
Conversion = ([polyolefin]0 − [polyolefin]t )/[polyolefin]0 × 100% tional frequencies of the lowest energy conformer of each molecule
were calculated at the B3LYP/6-311++G(d,p) level of theory using the
Gaussian suite of programs. INS spectra were obtained from calculated
Si = mi / ∑ mi × 100%
eigenvectors and eigenenergies using the aCLIMAX program45 and
compared with the experimental data.
Yield = conversion × Si × 100%
Simulation of 13C MAS NMR spectra of the reaction solid residue
has been conducted. Predicted 13C chemical shift was calculated on a

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platform based on DFT calculation46. On this platform, molecular con- Data Environment for Science. We thank Z. Wang for the assistance
struction and visualization modules are built using Ketcher, JSmol and during the acquisition of GD ESI mass spectra.
molview, three-dimensional conformation of two-dimensional molecu-
lar structures and the optimization of molecular structures based on Author contributions
Merck Molecular Force Field are performed using openbabel 2.3.1, and Z.C. carried out syntheses, characterization and catalytic tests of the
optimization of molecular structure based on DFT is performed using zeolite samples. W.H., W.W., W.Y., M.D., Z.M., F.L. and Y.L. participated in
Gaussian 09 at the M06-2X/6-31G(d) level. sample characterization. Z.C., Q.L., N.W. and J.X. carried out solid-state
NMR experiments. Z.C., W.W., W.Y., L.L., S.L., J.L., J.D., J.Z., P.F., D.C.G. and
Data availability G.H. collected and analysed NEXAFS data. Y.K., Z.C. and L.L. collected
All data are available in the main text or Supplementary Information. and analysed SANS data. S.Y., L.L., Z.C., Y.C., L.L.D. and A.J.R.-C.
Source data are provided with this paper. collected and analysed INS and DFT data. H.W., L.C. and Y.H. calculated
CO2 emission. X. H., S.Y., L.L. and B.H. directed and supervised the
References project. Z.C., X. H., S.Y., L.L. and B.H. prepared the manuscript.
44. Zhang, X. et al. Synthesis of self-pillared zeolite nanosheets by
repetitive branching. Science 336, 1684–1687 (2012). Competing interests
45. Ramirez-Cuesta, A. J. aCLIMAX 4.0.1, the new version of the The characterization of catalysts, catalytic method and catalytic
software for analyzing and interpreting INS spectra. Comput. results are described in a patent invented by L.L., Z.C. and B.H.
Phys. Commun. 157, 226–238 (2004). (Chinese patent, Institute of Chemistry, Chinese Academy of Sciences,
46. Li, Q., Tang, Y. & Xiang, J. An on-line NMR chemical shift prediction Longfei Lin, Ziyu Cen, Buxing Han, 202310750469.6, patent pending).
platform based on density functional theory. Chinese J. Magn. The other authors declare no competing interests.
Reson. 38, 22–31 (2021).
Additional information
Acknowledgements Extended data is available for this paper at
This work was supported by the National Natural Science Foundation https://doi.org/10.1038/s41557-024-01506-z.
of China (grant no. 22293012 to L.L., grant no. 22293015 to B.H.,
grant no. 22121002 to B.H.), Engineering and Physical Sciences Supplementary information The online version
Research Council (EPSRC) (grant no. EP/V056409/1 to S.Y.), the contains supplementary material available at
University of Manchester, Beijing National Laboratory for Molecular https://doi.org/10.1038/s41557-024-01506-z.
Sciences (BNLMS) and Peking University. We thank Beijing
Synchrotron Radiation Facility, Diamond Light Source and China Correspondence and requests for materials should be addressed to
Spallation Neutron Source for access to the beamlines 4B7B, B07-B Xue Han, Longfei Lin, Sihai Yang or Buxing Han.
(SI33962) and Small Angle Neutron Diffractometer, respectively.
A portion of this research used resources at the Spallation Neutron Peer review information Nature Chemistry thanks Jeff Armstrong and
Source, a Department of Energy (DOE) Office of Science User the other, anonymous, reviewer(s) for their contribution to the peer
Facility operated by Oak Ridge National Laboratory. The computing review of this work.
resources at Oak Ridge National Laboratory were made available
through the VirtuES and the ICE-MAN projects, funded by Laboratory Reprints and permissions information is available at
Directed Research and Development program and Compute and www.nature.com/reprints.

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Extended Data Fig. 1 | GC trace for commercial gasoline and gasoline obtained from conversion of HDPE. Reaction conditions: LSP-Z100, 0.09 g; HDPE, 0.45 g;
temperature, 240 °C; reaction time, 4 h; N2 atmosphere, 0.1 MPa. The ethanol in commercial gasoline is an additive.

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Article https://doi.org/10.1038/s41557-024-01506-z

Extended Data Fig. 2 | Trends of product yield in carbon numbers in the time course study. The profiles in (a) have been moved along Y axis, which only show trend
rather than absolute value. The profiles in (b) are plotted from original data and show the actual yields of species with certain carbon numbers.

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Article https://doi.org/10.1038/s41557-024-01506-z

Extended Data Fig. 3 | Standard mass spectrum of 2-methylbutane (a) of III@LSP-Z100 is because of dehydrogenation, oligomerisation of C6D14
and mass spectra of 2-methylbutane after the reaction on HZSM-5 (b) and and cleavage of the formed oligomers. Reaction conditions: catalyst, 0.075 g;
LSP-Z100 (c, d). The Mass spectra of GC peaks I@LSP-Z100 and III@LSP-Z100 in 2-methylbutane, 0.075 g; n-hexane (d-14), 0.15 g; temperature, 240 °C; reaction
GC traces show that I@LSP-Z100 is composed of i-C5H12 and i-C5H11D, and time, 1 hour; N2 atmosphere, 0.1 MPa.
III@LSP-Z100 is composed of i-C5D12, i-C5D11H and i-C5D10H2. The generation

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Article https://doi.org/10.1038/s41557-024-01506-z

Extended Data Fig. 4 | Standard mass spectrum of C6D14 (a) and mass spectra at m/z = 48 demonstrates the deuterated hexane has isomerized into deuterated
of deuterated hexane after reaction on HZSM-5 (b) and LSP-Z100 (c-e). 2-methylbutane. Reaction conditions: catalyst, 0.075 g; 2-methylbutane,
The Mass spectra show that II@LSP-Z100 is composed of C6D13H and C6D14, 0.075 g; n-hexane (d-14), 0.15 g; temperature, 240 °C; reaction time, 1 hour;
and IV@LSP-Z100 is composed of i-C6D13H and i-C6D12H2, and V@LSP-Z100 is N2 atmosphere, 0.1 MPa.
composed of C6D12H2 and C6D11H3. The base peak of IV@LSP-Z100 mass spectra

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Article https://doi.org/10.1038/s41557-024-01506-z

Extended Data Fig. 5 | Comparison of INS spectra of adsorbed 2-methylpentane (2-MP), 3-methylpentane (3-MP) and 1-butene (unsaturated oligomer) with
that of solid 2-MP, 3-MP and 1-butene. a, INS spectra of adsorbed 2-MP and solid 2-MP. b, INS spectra of adsorbed 3-MP and solid 3-MP. c, INS spectra of adsorbed
1-butene and solid 1-butene.

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